Substituted anionic compounds consisting of a backbone made up of a discrete number of saccharide units

ABSTRACT

The invention relates to substituted anionic compounds consisting of a backbone made up of a discrete number u of between 1 and 8 (1≦u≦8) of identical or different saccharide units, linked via identical or different glycosidic bonds, said saccharide units being chosen from the group consisting of hexoses in cyclic form or in open reduced form, which are randomly substituted. It also relates to the process for the preparation thereof and to the pharmaceutical compositions comprising same.

The present application is a continuation application of U.S. patentapplication Ser. No. 14/079,437 filed Nov. 13, 2013. The priorapplication is incorporated herein by reference in its entirety.

BACKGROUND

The present invention relates to anionic compounds intended fortherapeutic and/or prophylactic use, for the administration of an activeingredient or active ingredients to humans or to animals.

The anionic compounds according to the invention of which the backboneconsists of saccharide units comprising carboxyl groups are, owing totheir structure and their biocompatibility, undoubtedly of interest forthe pharmaceutical industry, in particular for stabilizing activeingredients, for example proteins.

Polysaccharides and/or oligosaccharides which have properties ofcreating interactions with active ingredients, for example proteins, areknown from WO 2008/038111 and WO 2010/041119, which are patentapplications filed in the name of Adocia.

In these patent applications, the polymers or oligomers are defined interms of their degree of polymerization DP, which is the average numberof repeating units (monomers) per polymer chain. It is calculated bydividing the number-average molar mass by the average mass of therepeated unit. They are also defined in terms of the chain lengthdistribution, also called the polydispersity index (Ip).

These polymers are therefore compounds consisting of chains of which thelengths are statistically variable, which are highly rich in possiblesites of interaction with protein active ingredients. Thismultiple-interaction potential could create a lack of specificity interms of interaction, whereas a smaller, better defined molecule couldmake it possible to be more specific in this respect.

Moreover, a polymer chain can interact with various sites present on aprotein ingredient, but can also, owing to the chain length, interactwith several protein ingredients, thereby leading to a bridgingphenomenon. This bridging phenomenon may, for example, result inaggregation of the proteins or in an increase in viscosity. The use of asmall molecule with a well-defined backbone makes it possible tominimize these bridging phenomena.

In addition, a molecule with a well-defined backbone is generally morereadily traceable (MS/MS, for example) in biological media duringpharmacokinetic or ADME (administration, distribution, metabolism,elimination) experiments compared with a polymer which generally gives avery diffuse signal with a high background noise in mass spectrometry.

SUMMARY OF INVENTION

In contrast, it is not out of the question for a well-defined andshorter molecule to possibly exhibit a shortage of possible sites ofinteraction with protein active ingredients.

Notwithstanding their perfectly defined structure, the anionic compoundsaccording to the invention consisting of a backbone made up of adiscrete number u of between 1 and 8 (1≦u≦8) of identical or differentsaccharide units also have the property of creating interactions withactive ingredients, protein active ingredients for example.

They nevertheless have particular properties with respect to certainactive ingredients which make them candidates of choice for preparingpharmaceutical formulations.

The functionalization of these anionic compounds with carboxyl groupsadvantageously makes it possible to modulate the interaction forcesinvolved between the anionic compound and the active ingredient.

By virtue of the defined structure of the backbone, thefunctionalization is easier and more precise and the nature of theanionic compounds obtained is therefore more homogeneous than when thebackbone is of polymeric nature.

The present invention thus aims to provide anionic compounds intendedfor the stabilization, administration and delivery of activeingredients, which can be prepared by methods that are relatively simpleto carry out. The objective of the present invention is thus to provideanionic compounds capable of enabling the stabilization, administrationand delivery of a large diversity of active ingredients.

The invention is also directed toward the obtaining of anionic compoundswhich can exhibit biodegradability that is sufficiently rapid andsuitable for their use in the preparation of a broad category ofpharmaceutical formulations, including for medicaments intended forchronic and/or high-frequency administration. In addition to therequirement of biodegradability that can be modulated afteradministration, the invention aims to provide anionic compounds whichcomply with the constrains established by the pharmaceutical industry,in particular in terms of stability under normal preservation andstorage conditions, and in particular in solution.

As will be demonstrated in the examples, the substituted anioniccompounds according to the invention make it possible to preparesolutions which are nonturbid in the presence of certain “model”proteins for formulation, such as lysozyme, which is not possible withcertain polymeric compounds, but are nevertheless capable of interactingwith model proteins such as albumin. This duality makes it possible tomodulate their properties and to obtain good excipient candidates forthe formulation of protein active ingredients without the drawbacksexhibited by some of the compounds described in the prior art.

BRIEF DESCRIPTION OF DRAWING

FIG. 1 is a mass spectrum of sodium N-phenylalaninate mannitolhexacarbamate.

DETAILED DESCRIPTION

The present invention relates to substituted anionic compounds, inisolated form or as a mixture, consisting of a backbone made up of adiscrete number u of between 1 and 8 (1≦u≦8) of identical or differentsaccharide units, linked via identical or different glycosidic bonds,said saccharide units being chosen from the group consisting ofpentoses, hexoses, uronic acids, N-acetylhexosamines in cyclic form orin open reduced form, characterized in that they are substituted with:

-   a) at least one substituent of general formula I:

—[R₁]_(a)-[[Q]-[R₂]_(n)]_(m)   formula I

-   the substituents being identical or different when there are at    least two substituents, in which:-   if n is equal to 0, then the radical -[Q]- is derived from a C₃ to    C₁₅ carbon-based chain which is optionally branched or substituted,    optionally unsaturated and/or optionally comprising one or more    ring(s) and/or comprising at least one heteroatom chosen from O, N    and S and at least one function L chosen from amine and alcohol    functions, said radical -[Q]- being attached to the backbone of the    compound by means of a linker arm R₁ to which it is bonded via a    function T, or directly bonded to the backbone via a function G,-   if n is equal to 1 or 2, then the radical -[Q]- is derived from a C₂    to C₁₅ carbon-based chain which is optionally branched or    substituted, optionally unsaturated and/or optionally comprising one    or more ring(s) and/or comprising at least one heteroatom chosen    from O, N and S and at least one function L chosen from amine and    alcohol functions and bearing n radical(s) R₂, said radical -[Q]-    being attached to the backbone of the compound by means of a linker    arm R₁ to which it is bonded via a function T, or directly bonded to    the backbone via a function G,-   the radical —R₁— being:-   either a bond and then a =0, and the radical -[Q]- is directly    bonded to the backbone via a function G,-   or a C₂ to C₁₅ carbon-based chain, and then a =1, which is    optionally substituted and/or comprising at least one heteroatom    chosen from O, N and S and at least one acid function before the    reaction with the radical -[Q]-, said chain being bonded to the    radical -[Q]- via a function T resulting from the reaction of the    acid function of the radical —R₁— with an alcohol or amine function    of the precursor of the radical -[Q]-, and said radical R₁ is    attached to the backbone by means of a function F resulting from a    reaction between a hydroxyl function or a carboxylic acid function    borne by the backbone and a function or a substituent borne by the    precursor of the radical —R₁—,-   the radical —R₂ is a C₁ to C₃₀ carbon-based chain which is    optionally branched or substituted, optionally unsaturated and/or    optionally comprising one or more ring(s) and/or one or more    heteroatom(s) chosen from O, N and S; it forms, with the radical    -[Q]-, a function Z resulting from a reaction between the alcohol,    amine or acid functions borne by the precursors of the radical —R₂    and of the radical -[Q]-.-   F is a function chosen from ether, ester, amide or carbamate    functions,-   T is a function chosen from amide or ester functions,-   Z is a function chosen from ester, carbamate, amide or ether    functions,-   G is a function chosen from ester, amide or carbamate functions,-   n is equal to 0, 1 or 2,-   m is equal to 1 or 2,-   the degree of substitution of the saccharide units, j, with    —[R₁]_(a)-[[Q]-[R₂]_(n)]_(m) being between 0.01 and 6, 0.01≦j≦6;-   b) and, optionally, one or more substituents —R′₁,

the substituent —R′₁ being a C₂ to C₁₅ carbon-based chain which isoptionally substituted and/or comprising at least one heteroatom chosenfrom O, N and S and at least one acid function in the form of an alkalimetal cation salt, said chain being bonded to the backbone via afunction F′ resulting from a reaction between a hydroxyl function or acarboxylic acid function borne by the backbone and a function or asubstituent borne by the precursor of the substituent —R′₁,

-   the degree of substitution of the saccharide units, i, with —R′₁    being between 0 and 6-j, 0≦i≦6-j and,-   if n≠0 and if the backbone does not bear anionic charges before    substitution, then i≠0,-   —R′₁ identical to or different than —R₁—,-   the free salifiable acid functions borne by —R′₁— are in the form of    alkali metal cation salts,-   F′ is a function chosen from ether, ester, amide or carbamate    functions,-   F, F′, T, Z and G being identical or different,-   i+j≦6.

In one embodiment, u is between 3 and 8.

In one embodiment, u is between 3 and 5.

In one embodiment, u is equal to 3.

In one embodiment, L is an amine function.

In one embodiment, L is an alcohol function.

In one embodiment, 0.05≦j≦6.

In one embodiment, 0.05≦j≦4.

In one embodiment, 0.1≦j≦3.

In one embodiment, 0.1≦j≦2.

In one embodiment, 0.2≦j≦1.5.

In one embodiment, 0.3≦j≦1.2.

In one embodiment, 0.5≦j≦1.2.

In one embodiment, 0.6≦j≦1.1.

In one embodiment, 0.25≦i≦3.

In one embodiment, 0.5≦i≦2.5.

In one embodiment, 0.6≦i≦2.

In one embodiment, 0.6≦i≦1.5.

In one embodiment, 0.6≦i≦1.1

In one embodiment, 0.3≦i+j≦6.

In one embodiment, 0.5≦i+j≦4.

In one embodiment, 0.5≦i+j≦3.

In one embodiment, 0.5≦i+j≦2.5.

In one embodiment, 1≦i+j≦2.

In one embodiment, m=2.

In one embodiment, m=1.

In one embodiment, n=2.

In one embodiment, n =1.

In one embodiment, n =0.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the radical -[Q]- is derived from an alpha-aminoacid.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the radical -[Q]- is derived from an alpha-aminoacid and n=0.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the alpha-amino acid is chosen from the groupcomprising alpha-methylphenylalanine, alpha-methyltyrosine,0-methyltyrosine, alpha-phenylglycine, 4-hydroxyphenylglycine and3,5-dihydroxyphenylglycine, in their L, D or racemic forms.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the alpha-amino acid is chosen from naturalalpha-amino acids.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the natural alpha-amino acid is chosen fromhydrophobic amino acids chosen from the group comprising tryptophan,leucine, alanine, isoleucine, glycine, phenylalanine, tyrosine andvaline, in their L, D or racemic forms.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the natural alpha-amino acid is chosen from polaramino acids chosen from the group comprising aspartic acid, glutamicacid, lysine, serine and threonine, in their L, D or racemic forms.

In one embodiment, the precursor of the radical -[Q]- is chosen fromdiamines.

In one embodiment, the precursor of the radical -[Q]- is chosen fromdiamines and n=1 or n=2.

In one embodiment, the diamines are chosen from the group consisting ofethylenediamine and lysine and its derivatives.

In one embodiment, the diamines are chosen from the gorup consisting ofdiethylene glycol diamine and triethylene glycol diamine.

In one embodiment, the precursor of the radical -[Q]- is chosen fromamino alcohols.

In one embodiment, the precursor of the radical -[Q]- is chosen fromamino alcohols and n=1 or n=2.

In one embodiment, the amino alcohols are chosen from the groupconsisting of ethanolamine, 2-aminopropanol, isopropanolamine,3-amino-1,2-propanediol, diethanolamine, diisopropanolamine,tromethamine (Tris) and 2-(2-aminoethoxy)ethanol.

In one embodiment, the precursor of the radical -[Q]- is chosen fromdialcohols.

In one embodiment, the precursor of the radical -[Q]- is chosen fromdialcohols and n=1 or n=2.

In one embodiment, the dialcohols are chosen from the group consistingof glycerol, diglycerol and triglycerol.

In one embodiment, the dialcohol is triethanolamine.

In one embodiment, the dialcohols are chosen from the group consistingof diethylene glycol and triethylene glycol.

In one embodiment, the dialcohols are chosen from the group consistingof polyethylene glycols.

In one embodiment, the precursor of the radical -[Q]- is chosen fromtrialcohols.

In one embodiment, the trialcohol is triethanolamine.

In one embodiment, when the radical -[Q]- is chosen from amino acids,the present invention relates to substituted anionic compounds, inisolated form or as a mixture, consisting of a backbone made up of adiscrete number u of between 1 and 8 (1≦u≦8) of identical or differentsaccharide units, linked via identical or different glycosidic bonds,said saccharide units being chosen from the group consisting ofpentoses, hexoses, uronic acids, N-acetylhexosamines in cyclic form orin open reduced form, characterized in that they are substituted with:

-   a) at least one substituent of general formula II:

—[R₁]_(a)-[[AA]-[R₂]_(n)]_(m)   formula II

-   the substituents being identical or different when there are at    least two substituents, in which:-   if n is equal to 0, then the radical -[AA]- denotes an amino acid    residue comprising a C₃ to C₁₅ carbon-based chain directly bonded to    the backbone via a function G′,-   if n is equal to 1 or 2, then the radical -[AA]- denotes an amino    acid residue comprising a C₂ to C₁₅ carbon-based chain bearing n    radical(s) —R₂ attached to the backbone of the compound by means of    a linker arm R₁ to which it is bonded via an amide function, or    directly bonded to the backbone via a function G′,-   the radical —R₁— being:    -   either a bond and then a=0, and the amino acid residue -[AA]- is        directly bonded to the backbone via a function G′,    -   or a C₂ to C₁₅ carbon-based chain, and then a=1, which is        optionally substituted and/or comprising at least one heteroatom        chosen from O, N and S and at least one acid function before the        reaction with the amino acid, said chain forming, with the amino        acid residue -[AA]-, an amide function, and is attached to the        backbone by means of a function F resulting from a reaction        between a hydroxyl function or a carboxylic acid function borne        by the backbone and a function or a substituent borne by the        precursor of the radical —R₁—,-   the radical —R₂ is a C₁ to C₃₀ carbon-based chain which is    optionally branched or substituted, optionally unsaturated and/or    optionally comprising one or more ring(s) and/or one or more    heteroatom(s) chosen from O, N or S; it forms, with the amino acid    residue -[AA]-, a function Z′ resulting from a reaction between a    hydroxyl, acid or amine function borne by the precursor of the    radical —R₂ and an acid, alcohol or amine function borne by the    precursor of the radical -[AA]-,-   F is a function chosen from ether, ester, amide or carbamate    functions,-   G′ is a function chosen from ester, amide or carbamate functions,-   Z′ is a function chosen from ester, amide or carbamate functions,-   n is equal to 0, 1 or 2,-   m is equal to 1 or 2,-   the degree of substitution of the saccharide units, j, with    —[R₁]_(a)-[[AA]-[R₂]_(n)]_(m) being between 0.01 and 6, 0.01≦j≦6;-   b) and, optionally, one or more substituents —R′₁,-   the substituent —R′₁ being a C₂ to C₁₅ carbon-based chain which is    optionally substituted and/or comprising at least one heteroatom    chosen from O, N and S and at least one acid function in the form of    an alkali metal cation salt, said chain being bonded to the backbone    via a function F′ resulting from a reaction between a hydroxyl    function or a carboxylic acid function borne by the backbone and a    function or a substituent borne by the precursor of the substituent    —r′₁,-   the degree of substitution of the saccharide units, i, with ′R′₁,    being between 0 and 6-j, 0≦i≦6-j, and    -   if n≠0 and if the backbone does not bear anionic charges before        substitution, then i≠0,-   —R′₁ identical to or different than —R₁—,    -   the free salifiable acid functions borne by the substituent —R′₁        are in the form of alkali metal cation salts,-   F′ is an ether, ester, amide or carbamate function,-   F, F′, G′ and Z′ are identical or different,-   i+j≦6.

In one embodiment, u is between 3 and 8.

In one embodiment, u is between 3 and 5.

In one embodiment, u is equal to 3.

In one embodiment, 0.05≦j≦6.

In one embodiment, 0.05≦j≦4.

In one embodiment, 0.1≦j≦3.

In one embodiment, 0.1≦j≦2.

In one embodiment, 0.2≦j≦1.5.

In one embodiment, 0.3≦j≦1.2.

In one embodiment, 0.5≦j≦1.2.

In one embodiment, 0.6≦j≦1.1.

In one embodiment, 0.25≦i≦3.

In one embodiment, 0.5≦i≦2.5.

In one embodiment, 0.6≦i≦2.

In one embodiment, 0.6≦i≦1.5.

In one embodiment, 0.6≦i≦1.1.

In one embodiment, 0.3≦i+j≦6.

In one embodiment, 0.5≦i+j≦4.

In one embodiment, 0.5≦i+j≦3.

In one embodiment, 0.5≦i+j≦2.5.

In one embodiment, 1≦i+j≦2.

In one embodiment, m=2.

In one embodiment, m=1.

In one embodiment, n=2.

In one embodiment, n=1.

In one embodiment, n=0.

In one embodiment, the present invention relates to substituted anioniccompounds consisting of a backbone made up of a discrete number u ofbetween 1 and 8 (1≦u≦8) of identical or different saccharide units,linked via identical or different glycosidic bonds, said saccharideunits being chosen from the group consisting of pentoses, hexoses,uronic acids, N-acetylhaxoamines in cyclic form or in open reduced form,characterized in that they are randomly substituted with:

-   a) at least one substituent of general formula II:

—[R₁]_(a)-[[AA]- [R₂]_(n)]_(m)   formula II

-   the substituents being identical or different when there are at    least two substituents, in which:-   the radical -[AA]- denotes an amino acid residue optionally bearing    n radical(s) R₂ attached to the backbone of the compound by means of    a linker arm R₁, or directly bonded to the backbone via a function    G′,-   —R₁— being:    -   either a bond and then a=0,    -   or a C₂ to C₁₅ carbon-based chain, and then a=1, which is        optionally substituted and/or comprising at least one heteroatom        chosen from O, N and S and at least one acid function before the        reaction with the amino acid, said chain forming, with the amino        acid residue -[AA]-, an amide bond, and is attached to the        backbone by means of a function F resulting from a reaction        between a hydroxyl function or a carboxylic acid function borne        by the backbone and a function borne by the precursor of —R₁—,-   the radical —R₂ is a C₁ to C₃₀ carbon-based chain which is    optionally branched or substituted, optionally unsaturated and/or    optionally comprising one or more ring(s) and/or one or more    heteroatom(s) chosen from O, N and S; it forms, with the amino acid    residue -[AA]-, a bond of ester, carbamate, amide or ether type    resulting from a reaction between a function borne by —R₂ and a    function borne by the precursor of the radical -[AA]-,-   F is an ether, ester, amide or carbamate function,-   G′ is an ester, amide or carbamate function,-   n is equal to 0, 1 or 2,-   m is equal to 1 or 2,-   the degree of substitution, j, with —[R₁]_(a)- [[AA]- [R₂ _(n)]_(m)    being between 0.01 and 6, 0.01≦j≦6;-   b) and, optionally, one or more substituents —R′₁,-   —R′₁ being a C₂ to C₁₅ carbon-based chain which is optionally    substituted and/or comprising at least one heteroatom chosen from O,    N and S and at least one acid function in the form of an alkali    metal cation salt, said chain being bonded to the backbone via a    function F′ resulting from a reaction between a hydroxyl function or    a carboxylic acid function borne by the backbone and a function    borne by the precursor of —R′₁,-   the degree of substitution i, with —R′₁, being between 0 and 6-j,    0≦i≦6-j and,    -   if n≠0 and if the backbone does not bear any anionic charges        before substitution, then i≠0,-   —R′₁ identical to or different than —R₁—,    -   the free salifiable acid functions borne by R′₁ are in the form        of alkali metal cation salts,-   F′ is an ether, ester, amide or carbamate function,-   F and F′ are identical or different,-   i+j≦6.

In one embodiment, u is between 3 and 5.

In one embodiment, u is equal to 3.

In one embodiment, 0.05≦j≦6.

In one embodiment, 0.05≦j≦4.

In one embodiment, 0.1≦j≦3.

In one embodiment, 0.1≦j≦2.

In one embodiment, 0.2≦j≦1.5.

In one embodiment, 0.3≦j≦1.2.

In one embodiment, 0.5≦j≦1.2.

In one embodiment, 0.6≦j≦1.1.

In one embodiment, 0.25≦i≦3.

In one embodiment, 0.5≦i≦2.5.

In one embodiment, 0.6≦i≦2.

In one embodiment, 0.6≦i≦1.5.

In one embodiment, 0.6≦i≦1.1.

In one embodiment, 0.3≦i+j≦6.

In one embodiment, 0.5≦i+k≦4.

In one embodiment, 0.5≦i+j≦3.

In one embodiment, 0.5≦i+j≦2.5.

In one embodiment, 1≦i+j≦2.

In one embodiment, m=2.

In one embodiment, m=1.

In one embodiment, n=2.

In one embodiment, n=1.

In one embodiment, n=0.

In one embodiment, the substituted anionic compound is chosen from thesubstituted anionic compounds, in isolated form or as a mixture,consisting of a backbone made up of a discrete number u of between 1 and8 (1≦u≦8) of identical or different saccharide units, linked viaidentical or different glycosidic bonds, said saccharide units beingchosen from the group consisting of hexoses, in cyclic form or in openreduced form, characterized in that they are substituted with:

-   a) at least one substituent of general formula V:

—[R₁]_(a)- [AA]_(m)   formula V

-   the substituents being identical or different when there are at    least two substituents, in which:-   the radical -[AA]- denotes an amino acid residue,-   the radical —R₁-being:    -   either a bond and then a=0, and the amino acid residue -[AA] is        directly bonded to the backbone via a function G_(a),    -   or a C₂ or C₁₅ carbon-based chain, and then a=1, which is        optionally substituted and/or comprising at least one heteroatom        chosen from O, N and S and at least one acid function before the        reaction with the amino acid, said chain forming, with the amino        acid residue -[AA], an amide function, and is attached to the        backbone by means of a function F_(a) resulting from a reaction        between a hydroxyl function borne by the backbone and a function        or a substituent borne by the precursor of the radical —R₁—,-   F_(a) is a function chosen from ether, ester or carbamate functions,-   G_(a) is a carbamate function,-   m is equal to 1 or 2,-   the degree of substitution of the saccharide units, j, with    —[R₁]_(a)- [AA]_(m) being strictly greater than 0 and less than or    equal to 6, 0<j≦6;-   b) and, optionally, one or more substituents —R′₁,-   the substituent —R′₁ being a C₂ to C₁₅ carbon-based chain which is    optionally substituted and/or comprising at least one heteroatom    chosen from O, N and S and at least one acid function in the form of    an alkali metal cation salt, said chain being bonded to the backbone    via a function F′_(a) resulting from a reaction between a hydroxyl    function or a carboxylic acid function borne by the backbone and a    function or a substituent borne by the precursor of the substituent    —R′₁,-   F′_(a) is an ether, ester or carbamate function,-   the degree of substitution of the saccharide units, i, with —R′₁,    being between 0 and 6-j, 0≦i≦6-j and,-   F_(a) and F_(a)′ are identical or different,-   F_(a) and G_(a) are identical or different,-   i+j≦6,-   —R′₁ identical to or different than —R₁—,-   the free salifiable acid functions borne by the substituent —R′₁ are    in the form of alkali metal cation salts,-   said identical or different glycosidic bonds being chosen from the    group consisting of glycosidic bonds of (1,1), (1,2), (1,3), (1,4)    or (1,6) type, in an alpha or beta geometry.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the radical -[AA]- is derived from an alpha-aminoacid.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the alpha-amino acid is chosen from the groupcomprising alpha-methylphenylalanine, alpha-methyltyrosine,0-methyltyrosine, alpha-phenylglycine, 4-hydroxyphenylglycine and3,5-dihydroxyphenylglycine, in their L, D or racemic forms.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the alpha-amino acid is chosen from naturalalpha-amino acids.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the natural alpha-amino acid is chosen fromhydrophobic amino acids chosen from the group comprising tryptophan,leucine, alanine, isoleucine, glycine, phenylalanine, tyrosine andvaline, in their L, D or racemic forms.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the natural alpha-amino acid is chosen from polaramino acids chosen from the group comprising aspartic acid, glutamicacid, lysine, serine and threonine, in their L, D or racemic forms.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I, II or V in which a is equal to 0.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which G is an ester function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which G is an amide function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which G is a carbamate function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstiteunts of formula II in which G′ is an ester function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstiteunts of formula II in which G′ is an amide function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which G′ is a carbamate function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I, II or V in which a is equal to 1.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II in which F is an ether function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II in which F is an ester function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II in which F is an amide function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II in which F is a carbamate function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula V in which F_(a) is an ether function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula V in which F_(a) is an ester function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula V in which F_(a) is a carabamate function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which T is an amide function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which T is an ester function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which T is an amide function, and F is anether function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which T is an amide function, and F is anester function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which T is an amide function, and F is acarbamate function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which T is an amide function, and F is anamide function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which T is an ester function, and F is anether function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which T is an ester function, and F is anester function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which T is an ester function, and F is acarabamate function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which T is an ester function, and F is anamide function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II in which F′ is an ether function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II in which F′ is an ester function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II in which F′ is an amide function. In oneembodiment, the substituted anionic compounds are characterized in thatthey are chosen from the anionic compounds substituted with substituentsof formula I or II in which F′ is a carbamate function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II in which F_(a) is an ether function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II in which F_(a) is an ester function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II in which F_(a) is a carbamate function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II in which F_(a)′ is an ether function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II in which F_(a)′ is an ester function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II in which F_(a)′ is a carbamate function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II in which F and F′ are identical.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II in which F and F′ are ether functions.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II in which F and F′ are ester functions.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II in which F and F′ are amide functions.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II in which F and F′ are carabamatefunctions.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II or V in which, when the radical —R₁— isa carbon-based chain, it optionally comprises a heteroatom chosen fromthe group consisting of O, N and S.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II or V in which the radical —R₁— is chosenfrom the radicals of formulae III and IV below:

in which:

-   -   o and p, which may be identical or different, are greater than        or equal to 1 and less than or equal to 12, and    -   R₃, R′₃, R₄ and R′₄, which may be identical or different, are        chosen from the group consisting of a hydrogen atom, a saturated        or unsaturated, linear, branched or cyclic C₁ to C₆ alkyl, a        benzyl, and a C₇ to C₁₀ alkyl-aryl and optionally comprising        heteroatoms chosen from the group consisting of O, N and/or S,        or functions chosen from the group consisting of carboxylic        acid, amine, alcohol or thiol functions.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II or V in which the radical —R₁—, beforeattachment to the radical -[AA]- or to the radical -[Q]-, is —CH₂—COOH,and after attachment is —CH₂—.

In one embodiment, the substituted compounds are characterized in thatthey are chosen from the anionic compounds substituted with substituentsof formula I or II or V in which the radical —R₁—, before attachment tothe radical -[AA]- or to the radical -[Q]-, is a C₂ to C₁₀ carbon-basedchain bearing a carboxylic acid group and, after attachment, is a C₂ toC₁₀ carbon-based chain.

In one embodiment, the substituted compounds are characterized in thatthey are chosen from the anionic compounds substituted with substituentsof formula I or II or V in which the radical —R₁—, before attachment tothe radical -[AA]- or to the radical -[Q]-, is a C₂ to C₁₀ carbon-basedchain bearing a carboxylic acid group and, after attachment, is a C₂ toC₁₀ carbon-based chain.

In one embodiment, the substituted compounds are characterized in thatthey are chosen from the anionic compounds substituted with substituentsof formula I or II or V in which the radical —R₁—, before attachment tothe radical -[AA]- or to the radical -[Q]-, is a C₂ to C₅ carbon-basedchain bearing a carboxylic acid group and, after attachment, is a C₂ toC₅ carbon-based chain.

In one embodiment, the substituted compounds are characterized in thatthey are chosen from the anionic compounds substituted with substituentsof formula I or II or V in which the radical —R₁—, before attachment tothe radical -[AA]- or to the radical -[Q]-, is a C₂ to C₅ carbon-basedchain bearing a carboxylic acid group and, after attachment, is a C₂ toC₅ carbon-based chain.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II or V in which the radical —R₁—, beforeattachment to the radical - [AA]- or to the radical -[Q]-, is chosenfrom the following groups, in which * represents the site of attachmentto F:

or their salts of alkali metal cations chosen from the group consistingof Na⁺ or K⁺.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II or V in which the radical —R₁—, beforeattachment to the radical -[AA]- or to the radical -[Q]-, is derivedfrom citric acid.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of the formula I or II or V in which the radical —R₁—,before attachment to the radical -[AA]- or to the radical -[Q]-, isderived from malic acid.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II or V and do not bear a substituent —R′₁.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II or V in which, when the substituent —R′₁is a carbon-based chain, it optionally comprises a heteroatom chosenfrom the group consisting of O, N and S.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II or V in which the substituent ′R′₁ ischosen from the radicals of formulae III and IV below:

in which:

-   -   o and p, which may be identical or different, are greater than        or equal to 1 and less than or equal to 12, and    -   R₃, R′₃, R₄ and R′₄, which may be identical or different, are        chosen from the group consisting of a hydrogen atom, a saturated        or unsaturated, linear, branched or cyclic C₁ to C₆ alkyl, a        benzyl and an alkyl-aryl and optionally comprising heteroatoms        chosen from the group consisting of O, N and/or S, or functions        chosen from the group consisting of carboxylic acid, amine,        alcohol or thiol functions.

In one embodiment, the substituted compounds are characterized in thatthey are chosen from the anionic compounds substituted with substituentsof formula I or II or V in which the substituent —R′₁ is —CH₂COOH.

In one embodiment, the substituted compounds are characterized in thatthey are chosen from the anionic compounds substituted with substituentsof formula I or II or V in which the radical —R′₁-, before attachment tothe radical -[AA]- or to the radical -[Q]-, is a C₂ to C₁₀ carbon-basedchain bearing a carboxylic acid group and after attachment is a C₂ toC₁₀ carbon-based chain.

In one embodiment, the substituted compounds are characterized in thatthey are chosen from the anionic compounds substituted with substituentsof formula I or II or V in which the radical —R′₁—, before attachment tothe radical -[AA]- or to the radical -[Q]-, is a C₂ to C₁₀ carbon-basedchain bearing a carboxylic acid group and after attachment is a C₂ toC₁₀ carbon-based chain.

In one embodiment, the substituted compounds are characterized in thatthey are chosen from the anionic compounds substituted with substituentsof formula I or II or V in which the radical —R′₁—, before attachment tothe radical -[AA]- or to the radical -[Q]-, is a C₂ to C₅ carbon-basedchain bearing a carboxylic acid group and after attachment is a C₂ to C₅carbon-based chain.

In one embodiment, the substituted compounds are characterized in thatthey are chosen from the anionic compounds substituted with substituentsof formula I or II or V in which the radical —R′₁—, before attachment tothe radical -[AA]- or to the radical -[Q]-, is a C₂ to C₅ carbon-basedchain bearing a carboxylic acid group and after attachment is a C₂ to C₅carbon-based chain.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II in which the substituent —R′₁ is chosenfrom the following groups, in which * represents the site of attachmentto F:

or their salts of alkali metal cations chosen from the group consistingof Na⁺ or K⁺.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula V in which the substituent —R′₁ is chosen fromthe following groups, in which * represents the site of attachment toF_(a):

or their salts of alkali metal cations chosen from the group consistingof Na⁺ or K⁺.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II or V in which the substituent —R′₁ isderived from citric acid.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II or V in which the substituent —R′₁ isderived from malic acid.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which Z is an ester function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which Z is an amide function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which Z is a carbamate function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which Z′ is an ester function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which Z′ is an amide function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which Z′ is a carbamate function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which Z is an ester function, T is an amidefunction, and F is an ether function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which Z is an ester function, T is an amidefunction, and F is an ester function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which Z is an ester function, T is an amidefunction, and F is a carbamate function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which Z is an ester function, T is an amidefunction, and F is an amide function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compound substituted withsubstituents of formula I in which Z is an ester function, T is an esterfunction, and F is an ether function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compound substituted withsubstituents of formula I in which Z is an ester function, T is an esterfunction, and F is an ester function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compound substituted withsubstituents of formula I in which Z is an ester function, T is an esterfunction, and F is a carba mate function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compound substituted withsubstituents of formula I in which Z is an ester function, T is an esterfunction, and F is an amide function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which Z is an amide function, T is an amidefunction, and F is an ether function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which Z is an amide function, T is an amidefunction, and F is an ester function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which Z is an amide function, T is an amidefunction, and F is a carbamate function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which Z is an amide function, T is an amidefunction, and F is an amide function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compound substituted withsubstituents of formula I in which Z is an amide function, T is an esterfunction, and F is an ether function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compound substituted withsubstituents of formula I in which Z is an amide function, T is an esterfunction, and F is an ester function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compound substituted withsubstituents of formula I in which Z is an amide function, T is an esterfunction, and F is a carbamate function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compound substituted withsubstituents of formula I in which Z is an amide function, T is an esterfunction, and F is an amide function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which Z is a carbamate function, T is anamide function, and F is an ether function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which Z is a carbamate function, T is anamide function, and F is an ester function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which Z is a carbamate function, T is anamide function, and F is a carbamate function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which Z is a carbamate function, T is anamide function, and F is an amide function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which Z is a carbamate function, T is anester function, and F is an ether function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which Z is a carbamate function, T is anester function, and F is an ester function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which Z is a carbamate function, T is anester function, and F is a carbamate function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which Z is a carbamate function, T is anester function, and F is an amide function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which G is an ester function and Z is anester function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which G is an amide function and Z is anester function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which G is a carbamate function and Z is anester function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which G is an ester function and Z is anamide function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which G is an amide function and Z is anamide function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which G is a carbamate function and Z is anamide function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which G is an ester function and Z is acarbamate function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which G is an amide function and Z is acarbamate function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which G is a carbamate function and Z is acarbamate function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which G′ is an ester function and Z′ is anester function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which G′ is an amide function and Z′ is anester function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which G′ is a carbamate function and Z′ isan ester function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which G′ is an ester function and Z′ is anamide function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which G′ is an amide function and Z′ is anamide function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which G′ is a carbamate function and Z′ isan amide function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which G′ is an ester function and Z′ is acarbamate function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which G′ is an amide function and Z′ is acarbamate function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which G′ is a carbamate function and Z′ isa carbamate function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II in which the radical —R₂ is a benzylradical.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II in which the radical —R₂ is derived froma hydrophobic alcohol.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the hydrophobic alcohol is chosen from alcoholsconsisting of an unsaturated and/or saturated, branched or unbranchedalkyl chain comprising from 4 to 18 carbon atoms.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the hydrophobic alcohol is chosen from alcoholsconsisting of an unsaturated and/or saturated, branched or unbranchedalkyl chain comprising from 6 to 18 carbon atoms.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the hydrophobic alcohol is chosen from alcoholsconsisting of an unsaturated and/or saturated, branched or unbranchedalkyl chain comprising from 8 to 16 carbon atoms.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the hydrophobic alcohol is octanol.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the hydrophobic alcohol is 2-ethylbutanol.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the hydrophobic alcohol is chosen from myristylalcohol, cetyl alcohol, stearyl alcohol, cetearyl alcohol, butyl alcoholand oleyl alcohol.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the hydrophobic alcohol is chosen from the groupconsisting of cholesterol and its derivatives.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the hydrophobic alcohol is cholesterol.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the hydrophobic alcohol is chosen from mentholderivatives.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the hydrophobic alcohol is menthol in its racemicform.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the hydrophobic alcohol is the D isomer ofmenthol.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the hydrophobic alcohol is the L isomer ofmenthol.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the hydrophobic alcohol is chosen fromtocopherols.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the tocopherol is alpha-tocopherol.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the alpha-tocopherol is the racemate ofalpha-tocopherol.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the tocopherol is the D isomer ofalpha-tocopherol.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the tocopherol is the L isomer of alphatocopherol.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the hydrophobic alcohol is chosen from alcoholsbearing an aryl group.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the alcohol bearing an aryl group is chosen fromthe group consisting of benzyl alcohol and phenethyl alcohol.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I or II in which the radical —R₂ is derived froma hydrophobic acid.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the hydrophobic acid is chosen from fatty acids.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the fatty acids are chosen from the groupconsisting of acids consisting of a saturated or unsaturated, branchedor unbranched alkyl chain comprising from 6 to 30 carbon atoms.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the fatty acids are chosen from the groupconsisting of linear fatty acids.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the linear fatty acids are chosen from the groupconsisting of caproic acid, enanthic acid, capyrlic acid, capric acid,nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, palmiticacid, stearic acid, arachidic acid, behenic acid, tricosanoic acid,lignoceric acid, heptacosanoic acid, octacosanoic acid and melissicacid.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the fatty acids are chosen from the groupconsisting of unsaturated fatty acids.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the unsaturated fatty acids are chosen from thegroup consisting of myristoleic acid, palmitoleic acid, oleic acid,elaidic acid, linoleic acid, alpha-linoleic acid, arachidonic acid,eicosapentaenoic acid, erucic acid and docosahexaenoic acid.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the fatty acids are chosen from the groupconsisting of bile acids and their derivatives.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the bile acids and their derivatives are chosenfrom the group consisting of cholic acid, dehydrocholic acid,deoxycholic acid and chenodeoxycholic acid.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 0, and the radical—R₁— and the substituent —R′₁, which are identical, are carbon-basedchains.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 0, and the radical-[AA]- is an amino acid residue.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 0, the radical —R₁—and the substituent —R′₁, which are identical, are carbon-based chainsand the radical -[AA]- is a phenylalanine residue.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 0, the radical —R₁—and the substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function and the radical -[AA]- is aphenylalanine residue.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 0, the radical —R₁—and the substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via a carbamate function and the radical -[AA]-is a phenylalanine residue.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 0, the radical —R₁—and the substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function and the radical -[AA]- is atryptophan residue.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 0, the radical —R₁—and the substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function and the radical -[AA]- is aleucine residue.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 0, the radical —R₁—and the substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function and the radical -[AA]- isan alpha-phenylglycine residue.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 0, the radical —R₁—and the substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function and the radical -[AA]- is atyrosine residue.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n and a are equal to 0.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n and a are equal to 0 and theradical -[AA]- is a phenylalanine residue directly bonded to thebackbone via a carbamate function.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which n is equal to 1, and the radical—R₁-and the substituent —R′₁, which are identical, are carbon-basedchains.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which n is equal to 1, the radical —R₁— andthe substituent —R′₁, which are identical, are carbon-based chains andthe radical -[Q]- is derived from a diamine.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which n is equal to 1, the radical —R₁— andthe substituent —R′₁, which are identical, are carbon-based chains, theradical -[Q]- is derived from a diamine and the radical —R₂ is derivedfrom a linear fatty acid.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which n is equal to 1, the radical —R₁— andthe substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function, the radical -[Q]- isderived from a diamine and the radical —R₂ is derived from a linearfatty acid

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which n is equal to 1, the radical —R₁— andthe substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function, the radical -[Q]- isderived from ethylenediamine and the radical —R₂ is derived from alinear fatty acid.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which n is equal to 1, the radical —R₁— andthe substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function, the radical -[Q]- isderived from ethylenediamine and the radical —R₂ is derived fromdodecanoic acid.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which n is equal to 1, the radical —R₁— andthe substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function, the radical -[Q]- isderived from a diamine and the radical —R₂ is derived from a hydrophobicalcohol.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which n is equal to 1, the radical —R₁-andthe substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function, the radical -[Q]- isderived from a diamine and the radical —R₂ is derived from cholesterol.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which n is equal to 1, the radical —R₁— andthe substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function, the radical -[Q]- isderived from ethylenediamine and the radical —R₂ is derived fromcholesterol.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which n is equal to 1, the radical —R₁— andthe substituent —R′₁, which are identical, are carbon-based chains, theradical —[Q]- is derived from an amino alcohol and the radical —R₂ isderived from a linear fatty acid.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which n is equal to 1, the radical —R₁— andthe substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function, the radical -[Q]- isderived from an amino alcohol and the radical —R₂ is derived from alinear fatty acid.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which n is equal to 1, the radical —R₁— andthe substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function, the radical -[Q]- isderived from ethanolamine and the radical —R₂ is derived from a linearfatty acid.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which n is equal to 1, the radical —R₁— andthe substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function, the radical -[Q]- isderived from ethanolamine and the radical —R₂ is derived from dodecanoicacid.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 1, and the radical—R₁— and the substituent —R′₁, which are identical, are carbon-basedchains.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 1, the radical —R₁—and the substituent —R′₁, which are identical, are carbon-based chainsand the radical —R₂ is derived from a linear fatty acid.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 1, the radical —R₁—and the substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function and the radical —R₂ isderived from a linear fatty acid.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 1, the radical —R₁—and the substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function, the radical -[AA]- is alysine residue and the radical —R₂ is derived from a linear fatty acid.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 1, the radical —R₁—and the substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function, the radical -[AA]- is alysine residue and the radical —R₂ is derived from dodecanoic acid.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compound substituted withsubstituents of formula II in which n is equal to 1, the radical —R₁—and the substituent —R′₁, which are identical, are carbon-based chainsand the radical —R₂ is derived from a hydrophobic alcohol.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compound substituted withsubstituents of formula II in which n is equal to 1, the radical —R₁—and the substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function and the radical —R₂ isderived from a hydrophobic alcohol.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 1, the radical —R₁—and the substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function, the radical -[AA]- is aleucine residue and the radical —R₂ is derived from a hydrophobicalcohol.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 1, the radical —R₁—and the substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function, the radical -[AA]- is aleucine residue and the radical —R₂ is derived from cholesterol.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 1, the radical —R₁—and the substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function, the radical -[AA]- is anaspartic acid residue and the radical —R₂ is derived from benzylalcohol.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 1, the radical —R₁—and the substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function, the radical -[AA]- is aglycine residue and the radical —R₂ is derived from decanol.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 1, the radical —R₁—and the substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function, the radical -[AA]- is aphenylalanine residue and the radical —R₂ is derived from3,7-dimethyloctanol.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 1 and a is equal to 0.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 1 and a is equal to 0and R₂ is a carbon-based chain.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 1 and a is equal to 0,the radical -[AA]- is a phenylalanine residue directly bonded to thebackbone via an amide function and R₂ is a carbon-based chain.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 1 and a is equal to 0,the radical -[AA]- is a phenylalanine residue directly bonded to thebackbone via an amide function and R₂ is derived from methanol.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which n is equal to 2, and the radical —R₁—and the substituent —R′₁, which are identical, are carbon-based chains.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which n is equal to 2, the radical —R₁— andthe substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function and the radical -[Q]- isderived from a diamine coupled to an amino acid.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which n is equal to 2, the radical —R₁— andthe substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function, the radical -[Q]- isderived from a diamine coupled to an amino acid and the radical R₂ isderived from a linear fatty acid.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which n is equal to 2, the radical —R₁— andthe substituent —R′₁, which are identical, are carbon-based chains, theradical -[Q]- is derived from ethylenediamine coupled to an amino acidand the radical R₂ is derived from a linear fatty acid.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which n is equal to 2, the radical —R₁— andthe substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function, the radical -[Q]- isderived from ethylenediamine coupled to a lysine and the radical R₂ isderived from a linear fatty acid.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which n is equal to 2, the radical —R₁— andthe substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function, the radical -[Q]- isderived from ethylenediamine coupled to a lysine and the radical R₂ isderived from dodecanoic acid.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which n is equal to 2, the radical —R₁— andthe substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function, the radical -[Q]- isderived from ethylenediamine coupled to a lysine and the radical R₂ isderived from dodecanoic acid.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula I in which n is equal to 2, the radical —R₁— andthe substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function, the radical -[Q]- isderived from ethylenediamine coupled to a lysine and the radical R₂ isderived from octanoic acid.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 2, and the radical—R₁— and the substituent —R′₁, which are identical, are carbon-basedchains.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 2, the radical —R₁—and the substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function and the radical —R₂ isderived from a hydrophobic alcohol.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 2, the radical —R₁—and the substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function, the radical -[AA]- is anaspartic acid residue and the radical —R₂ is derived from a hydrophobicalcohol.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 2, the radical —R₁—and the substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ether function, the radical -[AA]- is anaspartic acid residue and the radical —R₂ is derived from dodecanol.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal 2, the radical —R₁— andthe substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ester function and the radical —R₂ isderived from a hydrophobic alcohol.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 2, the radical —R₁—and the substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ester function, the radical -[AA]- is anaspartic acid residue and the radical —R₂ is derived from a hydrophobicalcohol.

In one embodiment, the substituted anionic compounds are characterizedin that they are chosen from the anionic compounds substituted withsubstituents of formula II in which n is equal to 2, the radical —R₁—and the substituent —R′₁, which are identical, are carbon-based chainsbonded to the backbone via an ester function, the radical -[AA]- is anaspartic acid residue and the radical —R₂ is derived from dodecanol.

In one embodiment, the substituted anionic compound in isolated formbears a substituent of general formula I or II or V.

In one embodiment, the substituted anionic compound in isolated formbears two substituents of general formula I or II or V.

In one embodiment, the substituted anionic compound in isolated formbears three substituents of general formula I or II or V.

In one embodiment, the substituted anionic compound in isolated formbears four substituents of general formula I or II or V.

In one embodiment, the substituted anionic compound in isolated formbears five substituents of general formula I or II or V.

In one embodiment, the substituted anionic compound in isolated formbears six substituents of general formula I or II or V.

In one embodiment, the substituted anionic compound in isolated formbears one substituent of general formula I or II or V per saccharideunit.

In one embodiment, the substituted anionic compound in isolated formbears two substituents of general formula I or II or V per saccharideunit.

In one embodiment, the substituted anionic compound in isolated formbears three substituents of general formula I or II or V per saccharideunit.

In one embodiment, the substituted anionic compound in isolated formbears four substituents of general formula I or II or V per saccharideunit.

In one embodiment, the anionic compounds according to the invention arecharacterized in that at least one saccharide unit is in cyclic form.

In one embodiment, the anionic compounds according to the invention arecharacterized in that at least one saccharide unit is in open reduced oropen oxidized form.

In one embodiment, the anionic compounds according to the invention arecharacterized in that at least one saccharide unit is chosen from thegroup of pentoses.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the pentoses are chosen from the group consistingof arabinose, ribulose, xylulose, lyxose, ribose, xylose, deoxyribose,arabitol, xylitol and ribitol.

In one embodiment, the anionic compounds according to the invention arecharacterized in that at least one saccharide unit is chosen from thegroup of hexoses.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the hexoses are chosen from the group consistingof mannose, glucose, fructose, sorbose, tagatose, psicose, galactose,allose, altrose, talose, idose, gulose, fucose, fuculose, rhamnose,mannitol, xylitol, sorbitol and galactitol (dulcitol).

In one embodiment, the anionic compounds according to the invention arecharacterized in that at least one saccharide unit is chosen from thegroup of uronic acids.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the uronic acids are chosen from the groupconsisting of glucuronic acid, iduronic acid, galacturonic acid,gluconic acid, mucic acid, glucaric acid and galactonic acid.

In one embodiment, the anionic compounds according to the invention arecharacterized in that at least one saccharide unit is anN-acetylhexosamine.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the N-acetylhexosamine is chosen from the groupconsisting of N-acetylgalactosamine, N-acetylglucosamine andN-acetylmannosamine.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the backbone is made up of a discrete number u=1of saccharide units.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the saccharide unit is chosen from the groupconsisting of hexoses in cyclic form or in open form.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the saccharide unit is chosen from the groupconsisting of glucose, mannose, mannitol, xylitol or sorbitol.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the saccharide unit is chosen from the groupconsisting of fructose and arabinose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the saccharide unit is N-acetylglucosamine.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the saccharide unit is N-acetylgalactosamine.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the saccharide unit is chosen from the groupconsisting of uronic acids.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the saccharide units are chosen from the groupconsisting of glucose, mannose, mannitol, xylitol or sorbitol.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the saccharide units are chosen from the groupconsisting of fructose and arabinose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that at least one of the saccharide units isN-acetylglucosamine.

In one embodiment, the anionic compounds according to the invention arecharacterized in that at least one of the saccharide units isN-acetylgalactosamine.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the backbone is made up of a discrete number 2 u 8of identical or different saccharide units.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical or different saccharide units, whichmake up the backbone made up of a discrete number 2 u 8 of saccharideunits, are chosen from the group of pentoses in cyclic form and/or inopen form.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical or different saccharide units, whichmake up the backbone made up of a discrete number 2≦u≦8 of saccharideunits, are chosen from the group of hexoses in cyclic form and/or inopen form.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical or different saccharide units, whichmake up the backbone made up of a discrete number 2≦u≦8 of saccharideunits, are chosen from the group consisting of uronic acids in cyclicform and/or in open form.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical or different saccharide units, whichmake up the backbone made up of a discrete number 2≦u≦8 of saccharideunits, are chosen from the group of hexoses and pentoses.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical or different saccharide units, whichmake up the backbone made up of a discrete number 2≦u≦8 of saccharideunits, are chosen from the group of hexoses.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical or different saccharide units, whichmake up the backbone made up of a discrete number 2≦u≦8 of saccharideunits, are hexoses chosen from the group consisting of glucose andmannose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the backbone is made up of a discrete number u=2of identical or different saccharide units.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the two saccharide units are identical.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the two saccharide units are different.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical or different saccharide units arechosen from hexoses and/or pentoses and are linked via a glycosidic bondof (1,1) type.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical or different saccharide units arechosen from hexoses and/or pentoses and are linked via a glycosidic bondof (1,2) type.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical or different saccharide units arechosen from hexoses and/or pentoses and are linked via a glycosidic bondof (1,3) type.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical or different saccharide units arechosen from hexoses and/or pentoses and are linked via a glycosidic bondof (1,4) type.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical or different saccharide units arechosen from hexoses and/or pentoses and are linked via a glycosidic bondof (1,6) type.

In one embodiment, the anionic compounds according to the invention arecharacterized in that they consist of a backbone made up of a discretenumber u=2 of identical or different saccharide units chosen fromhexoses linked via a glycosidic bond of (1,1) type.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the backbone made up of a discrete number u=2 ofdifferent saccharide units chosen from hexoses and linked via aglycosidic bond of (1,1) type is chosen from the group consisting oftrehalose and sucrose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that they consist of a backbone made up of a discretenumber u=2 of identical or different saccharide units chosen fromhexoses linked via a glycosidic bond of (1,2) type.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the backbone made up of a discrete number u=2 ofidentical or different saccharide units chosen from hexoses linked via aglycosidic bond of (1,2) type is kojibiose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that they consist of a backbone made up of a discretenumber u=2 of identical or different saccharide units chosen fromhexoses linked via a glycosidic bond of (1,3) type.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the backbone made up of a discrete number u=2 ofidentical or different saccharide units chosen from hexoses linked via aglycosidic bond of (1,3) type is chosen from the group consisting ofnigeriose and laminaribiose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that they consist of a backbone made up of a discretenumber u=2 of identical or different saccharide units chosen fromhexoses linked via a glycosidic bond of (1,4) type.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the backbone made up of a discrete number u=2 ofidentical or different saccharide units chosen from hexoses linked via aglycosidic bond of (1,4) type is chosen from the group consisting ofmaltose, lactose and cellobiose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that they consist of a backbone made up of a discretenumber u=2 of identical or different saccharide units chosen fromhexoses linked via a glycosidic bond of (1,6) type.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the backbone made up of a discrete number u=2 ofidentical or different saccharide units chosen from hexoses linked via aglycosidic bond of (1,6) type is chosen from the group consisting ofisomaltose, melibiose and gentiobiose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the backbone made up of a discrete number u=2 ofidentical or different saccharide units chosen from hexoses linked via aglycosidic bond of (1,6) type is isomaltose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that they consist of a backbone made up of a discretenumber u=2 of saccharide units of which one is in cyclic form and theother in open reduced form.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the backbone made up of a discrete number u=2 ofsaccharide units of which one is in cyclic form and the other in openreduced form is chosen from the group consisting of maltitol andisomaltitol.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the backbone is made up of a discrete number 3≦u≦8of identical or different saccharide units.

In one embodiment, the anionic compounds according to the invention arecharacterized in that at least one of the identical or differentsaccharide units, which make up the backbone made up of a discretenumber 3≦u≦8 of saccharide units, is chosen from the group consisting ofhexose and/or pentose units linked via identical or different glycosidicbonds.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical or different saccharide units, whichmake up the backbone made up of a discrete number 3≦u≦8 of saccharideunits, are chosen from hexoses and/or pentoses and are linked via atleast one glycosidic bond of (1,2) type.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical or different saccharide units, whichmake up the backbone made up of a discrete number 3≦u≦8 of saccharideunits, are chosen from hexoses and/or pentoses and are linked via atleast one glycosidic bond of (1,3) type.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical or different saccharide units, whichmake up the backbone made up of a discrete number 3≦u≦8 of saccharideunits, are chosen from hexoses and/or pentoses and are linked via atleast one glycosidic bond of (1,4) type.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical or different saccharide units, whichmake up the backbone made up of a discrete number 3≦u≦8 of saccharideunits, are chosen from hexoses and/or pentoses and are linked via atleast one glycosidic bond of (1,6) type.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the backbone is made up of a discrete number u=3of identical or different saccharide units.

In one embodiment, the anionic compounds according to the invention arecharacterized in that they comprise at least one saccharide unit chosenfrom the group consisting of hexoses in cyclic form and at least onesaccharide unit chosen from the group consisting of hexoses in openform.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the three saccharide units are identical.

In one embodiment, the anionic compounds according to the invention arecharacterized in that two of the three saccharide units are identical.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical saccharide units are chosen fromhexoses, two of which are in cyclic form and one of which is in openreduced form, and which are linked via glycosidic bonds of (1,4) type.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical saccharide units are chosen fromhexoses, two of which are in cyclic form and one of which is in openreduced form, and which are linked via glycosidic bonds of (1,6) type.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical or different saccharide units arechosen from hexoses and that the central hexose is linked via aglycosidic bond of (1,2) type and via a glycosidic bond of (1,4) type.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical or different saccharide units arechosen from hexoses and that the central hexose is linked via aglycosidic bond of (1,3) type and via a glycosidic bond of (1,4) type.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical or different saccharide units arechosen from hexoses and that the central hexose is linked via aglycosidic bond of (1,2) type and via a glycosidic bond of (1,6) type.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical or different saccharide units arechosen from hexoses and that the central hexose is linked via aglycosidic bond of (1,2) type and via a glycosidic bond of (1,3) type.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical or different saccharide units arechosen from hexoses and that the central hexose is linked via aglycosidic bond of (1,4) type and via a glycosidic bond of (1,6) type.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the backbone is erlose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the three identical or different saccharide unitsare hexose units chosen from the group consisting of mannose andglucose.

In one embodiment, the anionic compound according to the invention ischaracterized in that the backbone is maltotriose.

In one embodiment, the anionic compound according to the invention ischaracterized in that the backbone is isomaltotriose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the backbone is made up of a discrete number u=4of identical or different saccharide units.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the four saccharide units are identical.

In one embodiment, the anionic compounds according to the invention arecharacterized in that three of the four saccharide units are identical.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the four saccharide units are hexose units chosenfrom the group consisting of mannose and glucose.

In one embodiment, the anionic compound according to the invention ischaracterized in that the backbone is maltotetraose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical or different saccharide unit arechosen from hexoses and that a terminal hexose is linked via aglycosidic bond of (1,2) type and that the others are linked to oneanother via a glycosidic bond of (1,6) type.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical or different saccharide units arechosen from hexoses and are linked via a glycosidic bond of (1,6) type.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the backbone is made up of a discrete number u=5of identical or different saccharide units.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the five saccharide units are identical.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the five saccharide units are hexose units chosenfrom the group consisting of mannose and glucose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical or different saccharide units arechosen from hexoses and are linked via a glycosidic bond of (1,4) type.

In one embodiment, the anionic compound according to the invention ischaracterized in that the backbone is maltopentaose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the backbone is made up of a discrete number u=6of identical or different saccharide units.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the six saccharide units are identical.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical or different saccharide units arechosen from hexoses and are linked via a glycosidic bond of (1,4) type.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the six identical or different saccharide unitsare hexose units chosen from the group consisting of mannose andglucose.

In one embodiment, the anionic compound according to the invention ischaracterized in that the backbone is maltohexaose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the backbone is made up of a discrete number u=7of identical or different saccharide units.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the seven saccharide units are identical.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical or different saccharide units arechosen from hexoses and are linked via a glycosidic bond of (1,4) type.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the seven saccharide units are hexose units chosenfrom the group consisting of mannose and glucose.

In one embodiment, the anionic compound according to the invention ischaracterized in that the backbone is maltoheptaose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the backbone is made up of a discrete number u=8of identical or different saccharide units.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the eight saccharide units are identical.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the identical or different saccharide units arechosen from hexoses and are linked via a glycosidic bond of (1,4) type.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the eight saccharide units are hexose units chosenfrom the group consisting of mannose and glucose.

In one embodiment, the anionic compound according to the invention ischaracterized in that the backbone is maltooctaose.

In one embodiment, the anionic compound comprising a discrete number ofsaccharide units is a natural compound.

In one embodiment, the anionic compound comprising a discrete number ofsaccharide units is a synthetic compound.

In one embodiment, the anionic compounds according to the invention arecharacterized in that they are obtained by enzymatic degradation of apolysaccharide followed by purification.

In one embodiment, the anionic compounds according to the invention arecharacterized in that they are obtained by chemical degradation of apolysaccharide followed by purification.

In one embodiment, the anionic compounds according to the invention arecharacterized in that they are obtained chemically, by covalent couplingof lower-molecular-weight precursors.

In one embodiment, the anionic compounds according to the invention arecharacterized in that the backbone is sophorose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that they are chosen from the anionic compounds ofwhich the backbone is sucrose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that they are chosen from the anionic compounds ofwhich the backbone is lactulose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that they are chosen from the anionic compounds ofwhich the backbone is maltulose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that they are chosen from the anionic compounds ofwhich the backbone is leucrose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that they are chosen from the anionic compounds ofwhich the backbone is N-acetyllactosamine.

In one embodiment, the anionic compounds according to the invention arecharacterized in that they are chosen from the anionic compounds ofwhich the backbone is N-acetylallolactosamine.

In one embodiment, the anionic compounds according to the invention arecharacterized in that they are chosen from the anionic compounds ofwhich the backbone is rutinose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that they are chosen from the anionic compounds ofwhich the backbone is isomaltulose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that they are chosen from the anionic compounds ofwhich the backbone is fucosyllactose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that they are chosen from the anionic compounds ofwhich the backbone is gentianose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that they are chosen from the anionic compounds ofwhich the backbone is raffinose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that they are chosen from the anionic compounds ofwhich the backbone is melezitose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that they are chosen from the anionic compounds ofwhich the backbone is panose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that they are chosen from the anionic compounds ofwhich the backbone is kestose.

In one embodiment, the anionic compounds according to the invention arecharacterized in that they are chosen from the anionic compounds ofwhich the backbone is stachyose.

The nomenclature used hereinafter and in the examples section is asimplified nomenclature which refers back to the precursor of thefunctionalized compounds.

In one embodiment, an anionic compound according to the invention issodium maltotriosemethylcarboxylate functionalized with L-phenylalaninefor which i=1.0 and j=0.65.

In one embodiment, an anionic compound according to the invention issodium maltotriosemethylcarboxylate functionalized with L-phenylalaninefor which i=0.65 and j=1.0.

In one embodiment, an anionic compound according to the invention issodium maltotriosemethylcarboxylate functionalized with L-phenylalaninefor which i=0.35 and j=0.65.

In one embodiment, an anionic compound according to the invention issodium maltotriosemethylcarboxylate functionalized with L-tryptophan forwhich i=0.65 and j=1.0

In one embodiment, an anionic compound according to the invention issodium maltotriosemethylcarboxylate functionalized with cholesterylleucinate for which i=1.56 and j=0.09.

In one embodiment, an anionic compound according to the invention issodium N-methylcarboxylate mannitol carbamate modified withL-phenylalanine for which i=0.8 and j=3.5.

In one embodiment, an anionic compound according to the invention issodium N-phenylalaninate mannitol hexacarbamate for which i=0.0 andj=6.0.

In one embodiment, an anionic compound according to the invention issodium maltotriosemethylcarboxylate functionalized with L-phenylalaninefor which i=1.25 and j=0.4.

In one embodiment, an anionic compound according to the invention issodium maltotriosemethylcarboxylate functionalized with L-phenylalaninefor which i=0.8 and j=0.65.

In one embodiment, an anionic compound according to the invention issodium maltotriosemethylcarboxylate functionalized with L-phenylalaninefor which i=2.65 and j=0.65.

In one embodiment, an anionic compound according to the invention issodium maltopentaosemethylcarboxylate functionalized withL-phenylalanine for which i=1.0 and j=0.75.

In one embodiment, an anionic compound according to the invention issodium maltooctaosemethylcarboxylate functionalized with L-phenylalaninefor which i=1.0 and j=0.65.

In one embodiment, an anionic compound according to the invention issodium maltotriosemethylcarboxylate functionalized with cholesterylleucinate for which i=1.76 and j=0.08.

In one embodiment, an anionic compound according to the invention issodium maltotriosemethylcarboxylate functionalized with cholesterylleucinate for which i=1.33 and j=0.29.

In one embodiment, an anionic compound according to the invention issodium maltotriosemethylcarboxylate functionalized with cholesterylleucinate for which i=3.01 and j=0.29.

In one embodiment, an anionic compound according to the invention issodium maltopentaosemethylcarboxylate functionalized with cholesterylleucinate for which i=1.61 and j=0.14.

In one embodiment, an anionic compound according to the invention issodium maltooctaosemethylcarboxylate functionalized with cholesterylleucinate for which i=1.11 and j=0.09.

In one embodiment, an anionic compound according to the invention issodium maltotriosemethylcarboxylate functionalized with β-benzylaspartate for which i=1.15 and j=0.53.

In one embodiment, an anionic compound according to the invention issodium maltotriosemethylcarboxylate functionalized with dilaurylaspartate for which i=2.37 and j=0.36.

In one embodiment, an anionic compound according to the invention issodium maltotriosemethylcarboxylate functionalized with2-[(2-dodecanoylamino-6-dodecanoylamino)hexanoylamino]ethanamine forwhich i=2.52 and j=0.21.

In one embodiment, an anionic compound according to the invention issodium maltotriosemethylcarboxylate functionalized withN-(2-aminoethyl)dodecanamide for which i=1.37 and j=0.27.

In one embodiment, an anionic compound according to the invention issodium maltotriosesuccinate functionalized with dilauryl aspartate forwhich i=2.36 and j=0.41.

In one embodiment, an anionic compound according to the invention issodium maltotriosemethylcarboxylate functionalized with decanoylglycinate for which i=1.43 and j=0.21.

In one embodiment, an anionic compound according to the invention issodium maltotriosemethylcarboxylate functionalized with L-leucine forwhich i=1.06 and j=0.58.

In one embodiment, an anionic compound according to the invention issodium maltotriosemethylcarboxylate functionalized with cholesteryl2-aminoethylcarbamate for which i=2.45 and j=0.28.

In one embodiment, an anionic compound according to the invention issodium maltotriosemethylcarboxylate functionalized withalpha-phenylglycine for which i=1.12 and j=0.52.

In one embodiment, an anionic compound according to the invention issodium maltotriosemethylcarboxylate functionalized with2-[(2-octanoylamino-6-octanoylamino)hexanoylamino]ethanamine for whichi=1.36 and j=0.28.

In one embodiment, an anionic compound according to the invention issodium maltotriosemethylcarboxylate functionalized with L-tyrosine forwhich i=0.83 and j=0.81.

In one embodiment, an anionic compound according to the invention issodium maltotriosemethylcarboxylate functionalized with 2-aminoethyldodecanoate for which i=1.37 and j=0.27.

In one embodiment, an anionic compound according to the invention issodium maltotriosemethylcarboxylate functionalized with3,7-dimethyloctanoyl phenylalaninate for which i=1.25 and j=0.39.

In one embodiment, an anionic compound according to the invention issodium hyaluronate tetrasaccharide functionalized with methylphenylalaninate for which i=0.28 and j=0.22.

In one embodiment, an anionic compound according to the invention issodium maltotriosemethylcarboxylate functionalized with2-[(2-decanoylamino-6-decanoyl-amino)hexanoylamino]ethanamine for whichi=1.43 and j=0.21.

In one embodiment, an anionic compound according to the invention issodium maltotriosemethylcarboxylate functionalized withE-N-dodecanoyl-L-lysine for which i=1.27 and j=0.37.

In one embodiment, an anionic compound according to the invention issodium N-phenylalaninate mannitol 2,3,4,5-tetracarbamate for which i=0and j=4.

The invention also relates to the processes for producing substitutedanionic compounds, in isolated form or as a mixture, chosen from theanionic compounds substituted with substituents of formula I or II.

In one embodiment, the substituted anionic compounds chosen from theanionic compounds substituted with substituents of formula I or II arecharacterized in that they can be obtained by random grafting of thesubstituents onto the saccharide backbone.

In one embodiment, the substituted anionic compounds chosen from theanionic compounds substituted with substituents of formula I or II arecharacterized in that they can be obtained by grafting the substituentsat precise positions on the saccharide units by means of a process whichimplements steps of protection/deprotection of the alcohol or carboxylicacid groups naturally borne by the backbone. This strategy results inselective, in particular regioselective, grafting of the substituentsonto the backbone. The protective groups include, without limitation,those in the textbook described PGM Wuts, et al., Greene's ProtectiveGroups in Organic Synthesis 2007.

The saccharide backbone can be obtained by degradation of ahigh-molecular-weight polysaccharide. The degradation routes include,without limitation, chemical degradation and/or enzymatic degradation.

The saccharide backbone can also be obtained by formation of glycosidicbonds between monosaccharide or oligosaccharide molecules using anenzymatic or chemical coupling strategy. The coupling strategies includethose described in the publication JT Smoot et al., Advances inCarbohydrate Chemistry and Biochemistry 2009, 62, 162-250 and in thetextbook TK Lindhorst, Essentials of Carbohydrate Chemistry andBiochemistry 2007, 157-208. The coupling reactions can be carried out insolution or on a solid support. The saccharide molecules before couplingmay bear substituents of interest and/or be functionalized once randomlyor regioselectively coupled to one another.

Thus, by way of examples, the compounds according to the invention maybe obtained according to one of the following processes:

-   random grafting of the substituents onto a saccharide backbone;-   one or more steps of glycosylation between monosaccharide or    oligosaccharide molecules bearing substituents;-   one or more steps of glycosylation between one or more    monosaccharide or oligosaccharide molecules bearing substituents and    one or more monosaccharide or oligosaccharide molecules;-   one or more steps of introducing protective groups onto alcohols or    acids naturally borne by the saccharide backbone, followed by one or    more substituent grafting reactions and, finally, a step of removing    the protective groups;-   one or more steps of glycosylation between one or more    monosaccharide or oligosaccharide molecules bearing protective    groups on alcohols or acids naturally borne by the saccharide    backbone, one or more steps of grafting substituents onto the    backbone obtained, then a step of removing the protective groups;-   one or more steps of glycosylation between one or more    monosaccharide or oligosaccharide molecules bearing protective    groups on alcohols or acids naturally borne by the saccharide    backbone, and one or more monosaccharide or oligosaccharide    molecules, one or more substituent grafting steps, and then a step    of removing the protective groups.

The compounds according to the invention, isolated or as a mixture, canbe separated and/or purified in different ways after they have beenobtained, in particular by means of the processes described above.

Mention may in particular be made of chromatography methods, inparticular termed “preparative”, such as:

-   -   flash chromatography, in particular on silica, and    -   chromatography of the HPLC (high performance liquid        chromatography) type, in particular RP-HPLC or reverse phase        HPLC.

Selective precipitation methods can also be used.

The invention also relates to the use of the anionic compounds accordingto the invention for preparing pharmaceutical compositions.

The invention also relates to a pharmaceutical composition comprisingone of the anionic compounds according to the invention as previouslydescribed and at least one active ingredient.

The invention also relates to a pharmaceutical composition characterizedin that the active ingredient is chosen from the group consisting ofproteins, glycoproteins, peptides and nonpeptide therapeutic molecules.

The term “active ingredient” is intended to mean a product in the formof a single chemical entity and/or in the form of a combination having aphysiological activity. Said active ingredient may be exogenous, i.e. itis provided by the composition according to the invention. It may alsobe endogenous, for example growth factors which will be secreted into awound during the first healing phase and which may be kept on said woundby the composition according to the invention.

Depending on the pathological conditions targeted, it is intended forlocal and/or systemic treatment.

In the case of local and systemic releases, the modes of administrationenvisioned are via the intravenous, subcutaneous, intradermal,transdermal, intramuscular, oral, nasal, vaginal, ocular, buccal,pulmonary etc. route.

The pharmaceutical compositions according to the invention are either inliquid form, in an aqueous solution, or in the form of a powder, animplant or a film. They also comprise conventional pharmaceuticalexcipients well known to those skilled in the art.

Depending on the pathological conditions and the modes ofadministration, the pharmaceutical compositions may advantageously alsocomprise excipients for formulating them in the form of a gel, a sponge,an injectable solution, an oral solution, an orally disintegratingtablet, etc.

The invention also relates to a pharmaceutical composition,characterized in that it is administrable in the form of a stent, a filmor coating of implantable biomaterials, or an implant.

EXAMPLES

A. Preparation of the Compounds and Counterexamples

The structures of the compounds according to the invention are given intable 1. The structures of the counterexamples are given in table 2.

TABLE 1 Com- Substituent Substituent pounds i j Saccharide chain —R′₁—R₁—[[Q]—[R₂]_(n)]_(m) Compounds 1 to 6: R = H, R′₁,R₁—[[Q]—[R₂]_(n)]_(m) 1 1.0 0.65

2 0.65 1.0

3 0.35 0.65

4 0.65 1.0

5 1.56 0.09

6 0.8 3.5

Compound 7: R = R₁—[[Q]—[R₂]_(n)]_(m) 7 0 6

/

Compounds 8 to 30: R = R′₁, R₁—[[Q]—[R₂]_(n)]_(m) 8 1.25 0.4

9 0.8 0.65

10 2.65 0.65

11 1.0 0.75

12 1.0 0.65

13 1.76 0.08

14 1.33 0.29

15 3.01 0.29

16 1.61 0.14

17 1.11 0.09

18 1.15 0.53

19 2.37 0.36

20 2.52 0.21

21 1.37 0.27

22 2.36 0.41

23 1.43 0.21

24 1.06 0.58

25 2.45 0.28

26 1.12 0.52

27 1.36 0.28

28 0.83 0.81

29 1.37 0.27

30 1.25

Compound 31: R = ONa, [Q]—[R₂]_(n) 31 0.28 0.22

/

Compounds 32 to 33: R = H, R′₁, R₁—[[Q]—[R₂]_(n)]_(m) 32 1.43 0.21

33 1.27 0.37

Compound 34: R = H, R₁—[[Q]—[R₂]_(n)]_(m) 0 4

/

TABLE 2 Weight- Count- average er- molar exam- mass SubstituentSubstituent ples i j Saccharide chain (kg/mol) —R′₁ —R₁—[[AA]—[R₂]_(n)]Counter examples A1, A2, B1 and B2: R = H, R′₁, R₁—[[Q]]—R₂]_(n)]_(m) A11.0 0.65

1

A2 0.98 0.66

5

B1 1.64 0.05

1

B2 1.60 0.04

5

Compound 1: Sodium maltotriosemethylcarboxylate Functionalized withL-phenylalanine

0.6 g (16 mmol) of sodium borohydride is added to 8 g (143 mmol ofhydroxyl functions) of maltotriose (CarboSynth) dissolved in water at65° C. After stirring for 30 min, 28 g (238 mmol) of sodiumchloroacetate are added. 24 ml of 10N NaOH (240 mmol) are then addeddropwise to this solution and then the mixture is heated at 65° C. for90 minutes. 16.6 g (143 mmol) of sodium chloroacetate are then added tothe reaction medium, as are 14 ml of 10N NaOH (140 mmol), dropwise.After heating for 1 h, the mixture is diluted with water, neutralizedwith acetic acid and then purified by ultrafiltration on a 1 kDa PESmembrane against water. The compound concentration of the final solutionis determined by the dry extract, and then an acid/base assay in a 50/50(V/V) water/acetone mixture is carried out in order to determine thedegree of substitution with methylcarboxylate.

According to the dry extract: [compound]=32.9 mg/g.

According to the acid/base assay, the degree of substitution withmethylcarboxylate is 1.65 per glucoside unit.

The sodium maltotriosemethylcarboxylate solution is acidified on aPurolite (anionic) resin in order to obtain maltotriosemethylcarboxylicacid which is then lyophilized for 18 hours.

10 g of maltotriosemethylcarboxylic acid (63 mmol of methylcarboxylicacid functions) are solubilized in DMF and then cooled to 0° C. Amixture of ethyl phenylalaninate, hydrochloride salt (5.7 g; 25 mmol) inDMF is prepared. 2.5 g of triethylamine (25 mmol) are added to thismixture. A solution of NMM (6.3 g; 63 mmol) and of EtOCOCl (6.8 g, 63mmol) is then added to the mixture at 0° C. The ethyl phenylalaninatesolution is then added and the mixture is stirred at 10° C. An aqueousimidazole solution (340 g/I) is added and the mixture is then heated to30° C. The medium is diluted with water and then the solution obtainedis purified by ultrafiltration on a 1 kDa PES membrane against 0.1NNaOH, 0.9% NaCl and water. The compound concentration of the finalsolution is determined by the dry extract. A sample of solution islyophilized and analyzed by ¹H NMR in D₂O in order to determine thedegree of substitution with methylcarboxylates functionalized withphenylalanine.

According to the dry extract: [compound 1]=28.7 mg/g

According to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with phenylalanine per glycoside unitis 0.65.

The degree of substitution with sodium methylcarboxylates per glycosideunit is 1.0.

Compound 2: Sodium maltotriosemethylcarboxylate Functionalized withL-phenylalanine

Using a process similar to the one used for the preparation of compound1, a sodium maltotriosemethylcarboxylate functionalized withphenylalanine is obtained.

According to the dry extract: [compound 2]=29.4 mg/g

According to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with phenylalanine per glycoside unitis 1.0.

The degree of substitution with sodium methylcarboxylates per glycosideunit is 0.65.

Compound 3: Sodium maltotriosemethylcarboxylate Functionalized withL-phenylalanine

0.6 g (16 mmol) of sodium borohydride is added to 8 g (143 mmol ofhydroxyl functions) of maltotriose (CarboSynth) dissolved in water at65° C. After stirring for 30 min, 15 g (131 mmol) of sodiumchloroacetate are added. 24 ml of 10N NaOH (240 mmol) are then addeddropwise to this solution. After heating at 65° C. for 90 min, themixture is diluted with water, neutralized by adding acetic acid andthen purified by ultrafiltration on a 1 kDa PES membrane against water.The compound concentration of the final solution is determined by thedry extract, and then an acid/base assay in a 50/50 (V/V) water/acetonemixture is carried out in order to determine the degree of substitutionwith methylcarboxylate.

According to the dry extract: [compound]=20.1 mg/g.

According to the acid/base assay, the degree of substitution withmethylcarboxylate is 1.0 per glycoside unit.

The sodium maltotriosemethylcarboxylate solution is acidified on aPurolite (anionic) resin in order to obtain maltotriosemethylcarboxylicacid which is then lyophilized for 18 hours.

Using a process similar to the one used for the preparation of compound1, a sodium maltotriosemethylcarboxylate functionalized withphenylalanine is obtained.

According to the dry extract: [compound 3]=11.1 mg/g.

According to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with phenylalanine per glucoside unitis 0.65.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 0.35.

Compound 4: Sodium maltotriosemethylcarboxylate Funtionalized withL-tryptophan

Using a process similar to the one described in the preparation ofcompound 1, 10 g of maltotriosemethylcarboxylic acid having a degree ofsubstitution with methylcarboxylic acid of 1.65 per glucoside unit areobtained and then lyophilized.

10 g of maltotriosemethylcarboxylic acid (63 mmol of methylcarboxylicacid functions) are solubilized in DMF and then cooled to 0° C. Asolution of NMM (7.0 g; 69 mmol) and of EtOCOCl (7.5 g; 69 mmol) is thenadded. 11.5 g of L-tryptophan (Ajinomoto) (57 mmol) are then added andthe mixture is stirred at 10° C. An aqueous imidazole solution (340 g/I)is added and the mixture is then heated to 30° C. The mixture is dilutedwith water and the solution obtained is purified by ultrafiltration on a1 kDa PES membrane against 0.9% NaCl, 0.01N NaOH and water. The compoundconcentration of the final solution is determined by the dry extract. Asample of solution is lyophilized and analyzed by ¹H NMR in D₂O in orderto determine the degree of substitution with methylcarboxylatesfunctionalized with tryptophan.

According to the dry extract: [compound 4]=32.9 mg/g.

According to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with tryptophan per glucoside unit is1.0.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 0.65.

Compound 5: Sodium maltotriosemethylcarboxylate Functionalized withcholesteryl leucinate

Using a process similar to the one described in the preparation ofcompound 1, 10 g of maltotriosemethylcarboxylic acid having a degree ofsubstitution with methylcarboxylate of 1.65 per glucoside unit areobtained and then lyophilized.

Cholesteryl leucinate, para-toluenesulfonic acid salt, is preparepd fromcholesterol and leucine according to the process described in U.S. Pat.No. 4,826,818 (Kenji M., et al.).

10 g of maltotriosemethylcarboxylic acid (63 mmol of methylcarboxylicacid functions) are solubilized in DMF and then cooled to 0° C. Amixture of cholesteryl leucinate, para-toluenesulfonic acid salt (2.3 g;3 mmol) in DMF is prepared. 0.4 g of triethylamine (3 mmol) is added tothe mixture. Once the mixture reaches 0° C., a solution of NMM (1.9 g;19 mmol) and of EtOCOCl (2.1 g; 19 mmol) is added. After 10 minutes, thecholesteryl leucinate solution is added and the mixture is stirred at10° C. The mixture is then heated to 50° C. An aqueous imidazolesolution (340 g/I) is added and the medium is diluted with water. Theresulting solution is purified by ultrafiltration on a 1 kDa PESmembrane against 0.01N NaOH, 0.9% NaCl and water. The compoundconcentration of the final solution is determined by the dry extract. Asample of solution is lyophilized and analyzed by ¹H NMR in D₂O in orderto determine the degree of substitution with methylcarboxylates graftedwith cholesteryl leucinate.

According to the dry extract: [compound 5]=10.1 mg/g.

According to the ¹H NMR: the degree of substitution withmethylcarboxylates grafted with cholesteryl leucinate per glucoside unitis 0.09.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 1.56.

Compound 6: Sodium N-methylcarboxylate mannitol carbamate Modified withL-phenylalanine

8 g (131 mmol of hydroxyl functions) of mannitol (Fluka) are solubilizedin DMF at 80° C. After stirring for 30 minutes, DABCO(1,4-diazabicyclo[2.2.2]octane, 2.0 g; 18 mmol) and 9 ml of toluene areadded to the mixture which is brought to 120° C. with stirring andheteroazeotropically distilled. After the temperature of the reactionmixture has returned to 80° C., 34 g (263 mmol) of ethylisocyanatoacetate are gradually introduced. After 1.5 h of reaction, themedium is precipitated from an excess of water. The solid is filteredoff and saponified in an MeOH/THF mixture to which 265 ml of 1N NaOH areadded at ambient temperature. The solution is stirred overnight atambient temperature and then concentrated in a rotary evaporator. Theaqueous residue is acidified on a Purolite (anionic) resin in order toobtain mannitol N-methylcarboxylic acid.

The compound concentration of the final solution is determined by thedry extract, and then an acid/base assay in a 50/50 (V/V) water/acetonemixture is carried out in order to determine the degree of substitutionwith methylcarboxylate.

According to the dry extract: [compound]=27.4 mg/g.

According to the acid/base assay, the degree of substitution withmethylcarboxylate per molecule of mannitol is 4.3.

The mannitol N-methylcarboxylic acid solution is then lyophilized for 18hours.

10 g of mannitol N-methylcarboxylic acid (70 mmol of methylcarboxylicacid functions) are solubilized in DMF (14 g/I) and then cooled to 0° C.A mixture of ethyl phenylalaninate, hydrochloride salt (16 g; 70 mmol)in DMF is prepared (100 g/I). 7.1 g of triethylamine (70 mmol) are addedto this mixture. Once the mixture reaches 0° C., a solution of NMM (7.8g; 77 mmol) and of EtOCOCl (8.3 g; 77 mmol) is added. After 10 minutes,the ethyl phenylalaninate solution is added and the mixture is stirredat 10° C. An aqueous imidazole solution (340 g/I) is added. The solutionis then heated to 30° C. and then diluted by adding water. The solutionobtained is purified by ultrafiltration on a 1 kDa PES membrane against0.1 N NaOH, 0.9% NaCl and water. The compound concentration of the finalsolution is determined by the dry extract. A sample of solution islyophilized and analyzed by ¹H NMR in D₂O in order to determine thedegree of substitution with N-methylcarboxylates functionalized withphenylalanine.

According to the dry extract: [compound 6]=7.4 mg/g.

According to the ¹H NMR: the degree of substitution withN-methylcarboxylates functionalized with phenylalanine per molecule ofmannitol is 0.35.

The degree of substitution with sodium N-methylcarboxylates per moleculeof mannitol is 3.95.

Compound 7: Sodium N-phenylalaninate mannitol hexacarbamate

Ethyl L-phenylalaninate isocyanate is obtained according to the processdescribed in the publication Tsai, J.H. et al. Organic Syntheses 2004,10, 544-545, from ethyl L-phenylalanine hydrochloride (Bachem) andtriphosgene (Sigma).

0.91 g (5 mmol) of mannitol (Fluka) is dissolved in toluene and then 8.2g (37 mmol) of ethyl L-phenylalaninate isocyanate and 1 g (12.2 mmol) ofdiazabicyclo[2.2.2]octane (DABCO) are added. The mixture is heated at90° C. overnight. After concentration under vacuum, the medium isdiluted in dichloromethane and then washed with 1N HCl. The aqueousphase is extracted with dichloromethane and then the organic phases arecombined, dried and concentrated under vacuum. The ethylN-phenylalaninate mannitol hexacarbamate is isolated by flashchromatography (cyclohexane/ethyl acetate).

Yield: 4.34 g (58%).

¹H NMR (DMSO-d₆, ppm): 0.75-1.25 (6H); 2.75-3.15 (12H); 3.7-4.4 (22H);4.8-5.2 (4H); 7.1-7.35 (30H); 7.4-7.85 (6H).

MS (ESI): 1497.7 ([M+H]⁺); ([M+H]⁺ calculated: 1498.7).

22.1 ml of 2N NaOH are added to 10.7 g (7.14 mmol) of ethylN-phenylalaninate mannitol hexacarbamate dissolved in a tetrahydrofuran(THF)/ethanol/water mixture and the mixture is stirred at roomtemperature for 3 h. After evaporation of the THF and ethanol undervacuum, the residual aqueous phase is washed with dichloromethane,concentrated under vacuum and acidified with 2N HCl. The suspension iscooled to 0° C. and filtered, and then the white solid ofN-phenylalanine acid mannitol hexacarbamate obtained is thoroughlywashed with water and then dried under vacuum.

Yield: 9.24 g (97%).

¹H NMR (DMSO-d₆, TFA-d₁, ppm): 2.6-3.25 (12H); 3.8-4.3 (10H); 4.75-5.0(4H); 7.0-7.75 (36H).

MS (ESI): 1329.6 ([M+H]⁺); ([M+H]⁺ calculated: 1330.4).

The N-phenylalanine acid mannitol hexacarbamate is dissolved in water(50 g/I) and neutralized by gradually adding 10N sodium hydroxide inorder to give an aqueous solution of sodium N-phenylalaninate mannitolhexacarbamate which is then lyophilized.

¹H NMR (D₂O, ppm): 2.6-3.25 (12H); 3.8-4.3 (10H); 4.75-5.0 (4H); 6.9-7.5(30H). LC/MS (CH₃CN/H₂O/HCO₂H (10 mM), ELSD, ESI in negative mode):1328.4 ([M-1]); ([M-1] calculated: 1328.3). This mass spectrum is shownin FIG. 1.

Compound 8: Sodium maltotriosemethylcarboxylate Functionalized withL-phenylalanine

Using a process similar to the one used for the preparation of compound1, a sodium maltotriosemethylcarboxylate functionalized withphenylalanine is obtained.

According to the dry extract: [compound 8]=10.9 mg/g.

According to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with phenylalanine per glucoside unitis 0.40.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 1.25.

Compound 9: Sodium maltotriosemethylcarboxylate Functionalized withL-phenylalanine

0.6 g (16 mmol) of sodium borohydride is added to 8 g (143 mmol ofhydroxyl functions) of maltotriose (CarboSynth) dissolved in water at65° C. After stirring for 30 min, 28 g (237 mmol) of sodiumchloroacetate are added. 24 ml of 10N NaOH (240 mmol) are then addeddropwise to this solution. After heating at 65° C. for 90 min, themixture is diluted with water, neutralized by adding acetic acid andthen purified by ultrafiltration on a 1 kDa PES membrane against water.The compound concentration of the final solution is determined by thedry extract, and then an acid/base assay in a 50/50 (V/V) water/acetonemixture is carried out in order to determine the degree of substitutionwith methylcarboxylate.

According to the dry extract: [compound]=14.5 mg/g.

According to the acid/base assay, the degree of substitution withmethylcarboxylate is 1.45 per glucoside unit.

The sodium maltotriosemethylcarboxylate solution is acidified on aPurolite (anionic) resin in order to obtain maltotriosemethylcarboxylicacid which is then lyophilized for 18 hours.

Using a process similar to the one used for the preparation of compound1, a sodium maltotriosemethylcarboxylate functionalized withphenylalanine is obtained.

According to the dry extract: [compound 9]=10.8 mg/g.

According to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with phenylalanine per glucoside unitis 0.65.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 0.8.

Compound 10: Sodium maltotriosemethylcarboxylate Functionalized withL-phenylalanine

Using a process similar to the one described in the preparation ofcompound 1, 8 g of sodium maltotriosemethylcarboxylate characterized bya degree of substitution with sodium methylcarboxylate of 1.76 aresynthesized and lyophilized.

8 g (58 mmol of hydroxyl functions) of the lyophilisate and 15 g (129mmol) of sodium chloroacetate are dissolved in water at 65° C. 13 ml of10N NaOH (130 mmol) are added dropwise to this solution and then themixture is heated at 65° C. for 90 minutes. 9 g (78 mmol) of sodiumchloroacetate are then added to the reaction medium, as are 8 ml of 10NNaOH (80 mmol), dropwise. After heating for 1 h, the mixture is dilutedwith water, neutralized with acetic acid and then purified byultrafiltration on a 1 kDa PES membrane against water. The compoundconcentration of the final solution is determined by the dry extract,and then an acid/base assay in a 50/50 (V/V) water/acetone mixture iscarried out in order to determine the degree of substitution with sodiummethylcarboxylate

According to the dry extract: [compound]=11.7 mg/g.

According to the acid/base assay, the degree of substitution with sodiummethylcarboxylate is 3.30.

The sodium maltotriosemethylcarboxylate solution is acidified on aPurolite (anionic) resin in order to obtain maltotriosemethylcarboxylicacid which is then lyophilized for 18 hours.

Using a process similar to the one used for the preparation of compound1, a sodium maltotriosemethylcarboxylate functionalized withphenylalanine is obtained.

According to the dry extract: [compound 10]=14.9 mg/g.

According to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with phenylalanine per glucoside unitis 0.65.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 2.65.

Compound 11: Sodium maltopentaosemethylcarboxylate Functionalized withL-phenylalanine

Using a process similar to the one described in the preparation ofcompound 1, but carried out with maltopentaose (CarboSynth), 10 g ofmaltopentaosemethylcarboxylic acid having a degree of substitution withmethylcarboxylic acid of 1.75 per glucoside unit are obtained and thenlyophilized.

Using a process similar to the one used for the preparation of compound1, a sodium maltopentaosemethylcarboxylate functionalized withphenylalanine is obtained.

According to the dry extract: [compound 11]=7.1 mg/g.

According to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with phenylalanine per glucoside unitis 0.75.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 1.0.

Compound 12: Sodium maltooctaosemethylcarboxylate Functionalized withL-phenylalanine

Using a process similar to the one described in the preparation ofcompound 1, but carried out with maltooctaose (CarboSynth), 10 g ofmaltooctaosemethylcarboxylic acid having a degree of substitution withmethylcarboxylic acid of 1.65 per glucoside unit are obtained and thenlyophilized.

Using a process similar to the one used for the preparation of compound1, a sodium maltooctaosemethylcarboxylate functionalized withphenylalanine is obtained.

According to the dry extract: [compound 12]=26.3 mg/g.

According to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with phenylalanine per glucoside unitis 0.65.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 1.0.

Compound 13: Sodium maltotriosemethylcarboxylate Functionalized withcholesteryl leucinate

Using a process similar to the one described in the preparation ofcompound 5, a sodium maltotriosemethylcarboxylate, characterized by adegree of substitution with sodium methylcarboxylate of 1.84, isfunctionalized with cholesteryl leucinate.

According to the dry extract: [compound 13]=10.1 mg/g.

According to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with cholesteryl leucinate is 0.08.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 1.76.

Compound 14: Sodium maltotriosemethylcarboxylate Functionalized withcholesteryl leucinate

Using a process similar to the one described in the preparation ofcompound 5, a sodium maltotriosemethylcarboxylate, characterized by adegree of substitution with sodium methylcarboxylate of 1.62, isfunctionalized with cholesteryl leucinate.

According to the dry extract: [compound 14]=29.4 mg/g.

According to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with cholesteryl leucinate is 0.29.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 1.33.

Compound 15: Sodium maltotriosemethylcarboxylate Functionalized withcholesteryl leucinate

Using a process similar to the one described in the preparation ofcompound 10, 10 g of maltotriosemethylcarboxylic acid having a degree ofsubstitution with methylcarboxylic acid of 3.30 per glucoside unit areobtained and then lyophilized.

Using a process similar to the one described in the preparation ofcompound 5, a sodium maltotriosemethylcarboxylate, characterized by adegree of substitution with sodium methylcarboxylate of 3.30, isfunctionalized with cholesteryl leucinate.

According to the dry extract: [compound 15]=13.1 mg/g.

According to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with cholesteryl leucinate is 0.29.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 3.01.

Compound 16: Sodium maltopentaosemethylcarboxylate Functionalized withcholesteryl leucinate

Using a process similar to the one described in the preparation ofcompound 11, 10 g of maltopentaosemethylcarboxylic acid, characterizedby a degree of substitution with methylcarboxylic acid of 1.75, aresynthesized and then lyophilized.

Using a process similar to the one described in the preparation ofcompound 5, a sodium maltopentaosemethylcarboxylate functionalized withcholesteryl leucinate is obtained.

According to the dry extract: [compound 16]=10.9 mg/g.

According to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with cholesteryl leucinate is 0.14.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 1.61.

Compound 17: Sodium maltooctaosemethylcarboxylate Functionalized withcholesteryl leucinate

Using a process inspired by the one described in the preparation ofcompound 12, 10 g of maltooctaosemethylcarboxylic acid, characterized bya degree of substitution with methylcarboxylic acid of 1.2, aresynthesized and then lyophilized.

Using a process similar to the one described in the prepartion ofcompound 5, a sodium maltooctaosemethylcarboxylate functionalized withcholesteryl leucinate is obtained.

According to the dry extract: [compound 17]=14.7 mg/g.

According to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with cholesteryl leucinate is 0.09.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 1.11.

Compound 18: Sodium maltotriosemethylcarboxylate Functionalized withβ-benzyl aspartate

Using a process similar to the one described in the preparation ofcompound 1, 10 g of maltotriosemethylcarboxylic acid having a degree ofsubstitution with methylcarboxylic acid of 1.68 per glucoside unit areobtained and then lyophilized.

6 g of maltotriosemethylcarboxylic acid (38 mmol of methylcarboxylicacid functions) are solubilized in DMF and then cooled to 0° C. Amixture of β-benzyl aspartate (Bachem, 3.5 g; 16 mmol) and oftriethylamine (16 mmol) is prepared in water. A solution of NMM (3.2 g;32 mmol) and of EtOCOCl (3.4 g, 32 mmol) is then added to themaltotriosemethylcarboxylic acid solution at 0° C. The solution ofbenzyl aspartate and of triethylamine is then added and the mixture isstirred at 30° C. An aqueous imidazole solution (340 g/I) is added after90 minutes. The medium is diluted with water and then the solutionobtained is purified by ultrafiltration on a 1 kDa PES membrane againsta 150 mM NaHCO₃/Na₂CO₃ buffer, pH 10.4, 0.9% NaCl and water. Thecompound concentration of the final solution is determined by the dryextract. A sample of solution is lyophilized and analyzed by ¹H NMR inD₂O in order to determine the degree of substitution withmethylcarboxylates functionalized with β-benzyl aspartate.

According to the dry extract: [compound 18]=15.0 mg/g.

Accoridng to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with β-benzyl aspartate per glucosideunit is 0.53.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 1.15.

Compound 19: Sodium maltotriosemethylcarboxylate Functionalized withdilauryl aspartate

Dilauryl aspartate, para-toluenesulfonic acid salt, is prepared fromdodecanol and aspartic acid according to the process described in U.S.Pat. No. 4,826,818 (Kenji M., et al.).

Using a process inspired by the one described in the preparation ofcompound 10, 10 g of maltotriosemethylcarboxylic acid having a degree ofsubstitution with methylcarboxylic acid of 2.73 per glucoside unit areobtained and then lyophilized.

Using a process similar to the one described in the preparation ofcompound 5, a sodium maltotriosemethylcarboxylate, characterized by adegree of substitution with sodium methylcarboxylate of 2.73, isfunctionalized with dilauryl aspartate in DMF. The medium is dilutedwith water and then the solution obtained is purified by dialysis on a3.5 kDa cellulose membrane against a 150 mM NaHCO₃/Na₂CO₃ buffer, pH10.4, 0.9% NaCl and water. The compound concentration of the finalsolution is determined by means of the dry extract. A sample of solutionis lyophilized and analyzed by ¹H NMR in D₂O in order to determine thedegree of substitution with methylcarboxylates functionalized withdilauryl aspartate.

According to the dry extract: [compound 19]=3.4 mg/g.

According to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with dilauryl aspartate is 0.36.

The degree of substitutio with sodium methylcarboxylates per glucosideunit is 2.37.

Compound 20: Sodium maltotriosemethylcarboxylate Functionalized with2-[(2-dodecanoylamino-6-dodecanoylamino)hexanoylamino]ethanamine

The methyl ester of N,N-bis(dodecanoyl)lysine is obtained according tothe process described in the publication Pal, A et al., Tetrahedron2007, 63, 7334-7348, from the methyl ester of L-lysine, hydrochloricacid salt (Bachem) and from dodecanoic acid (Sigma). The2-[(2-dodecanoylamino-6-dodecanoylamino)hexanoylamino]ethanamine isobtained according to the process described in U.S. Pat. No. 2,387,201(Weiner et al.), from the methyl ester of N,N-bis(dodecanoyl)lysine andfrom ethylenediamine (Roth).

Using a process similar to the one described in the preparation ofcompound 10, 10 g of maltotriosemethylcarboxylic acid having a degree ofsubstitution with methylcarboxylic acid of 2.73 per glucoside unit areobtained and then lyophilized.

Using a process similar to the one described in the preparation ofcompound 19, a sodium maltotriosemethylcarboxylate, characterized by adegree of substitution with sodium methylcarboxylate of 2.73, isfunctionalized with2-[(2-dodecanoylamino-6-dodecanoylamino)hexanoylamino]ethanamine.

According to the dry extract: [compound 20]=2.4 mg/g.

According to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with2-[(2-dodecanoylamino-6-dodecanoylamino)hexanoyl-amino]ethanamine is0.21.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 2.52.

Compound 21: Sodium maltotriosemethylcarboxylate Functionalized withN-(2-aminoethyl)dodecanamide

The N-(2-aminoethyl)dodecanamide is obtained according to the processdescribed in U.S. Pat. No. 2,387,201 (Weiner et al.), from the methylester of dodecanoic acid (Sigma) and from ethylenediamine (Roth).

Using a process similar to the one described in the preparation ofcompound 10 g of maltotriosemethylcarboxylic acid having a degree ofsubstitution with methylcarboxylic acid of 1.64 per glucoside unit areobtained and then lyophilized.

Using a process similar to the one described in the preparation ofcompound 19, a sodium maltotriosemethylcarboxylate, characterized by adegree of substitution with sodium methylcarboxylate of 1.64, isfunctionalized with N-(2-aminoethyl)dodecanamide.

According to the dry extract: [compound 21]=2.4 mg/g.

According to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with N-(2-aminoethyl)dodecanamide is0.27.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 1.37.

Compound 22: Sodium maltotriosesuccinate Functionalized with dilaurylaspartate

25 g (i.e. 0.543 mol of hydroxyl functions) of maltotriose aresolubilized in 62 ml of DMSO at 60° C., and then the temperature isprogrammed at 40° C. 59.3 g (0.592 mmol) of succinic anhydride insolution in 62 ml of DMF and 59.9 g (0.592 mmol) of NMM, diluted in 62ml of DMF, are added to this solution. After 3 h of reaction, thereaction medium is diluted in water (67 ml) and the oligosaccharide ispurified by ultrafiltration. The molar fraction of succinic ester formedper glucoside unit is 2.77 according to the ¹H NMR in D₂O/NaOD.

The sodium maltotriosesuccinate solution is acidified on a Purolite(anionic) resin in order to obtain maltotriosesuccinic acid which isthen lyophilized for 18 hours.

Using a process similar to the one described in the preparation ofcompound 19, a sodium maltotriosesuccinate, characterized by a degree ofsubstitution with sodium succinate of 2.77, is functionalized withdilauryl aspartate.

According to the dry extract: [compound 22]=12.9 mg/g.

According to the ¹H NMR: the degree of substitution with succinatesfunctionalized with dilauryl aspartate is 0.41.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 2.36.

Compound 23: Sodium maltotriosemethylcarboxylate Functionalized withdecanoyl glycinate

The decanoyl glycinate, para-toluenesulfonic acid salt, is prepared fromdecanol and from glycine according to the process described in U.S. Pat.No. 4,826,818 (Kenji M., et al.).

Using a process similar to the one described in the preparation ofcompound 21, a sodium maltotriosemethylcarboxylate, characterized by adegree of substitution with sodium methylcarboxylate of 1.64, isfunctionalized with decanoyl glycinate.

According to the dry extract: [compound 23]=2.4 mg/g.

According to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with decanoyl glycinate is 0.21.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 1.43.

Compound 24: Sodium maltotriosemethylcarboxylate Functionalized withL-leucine

Using a process similar to the one described in the preparation ofcompound 18, but involving L-leucine (Roth), a sodiummaltotriosemethylcarboxylate, characterized by a degree of substitutionwith sodium methylcarboxylate of 1.64, is functionalized with L-leucine.

According to the dry extract: [compound 24]=2.3 mg/g.

According to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with L-leucine is 0.58.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 1.06.

Compound 25: Sodium maltotriosemethylcarboxylate Functionalized withcholesteryl 2-aminoethylcarbamate

The cholesteryl 2-aminoethylcarbamate, hydrochloric acid salt, isprepared according to the process as described in patent WO 2010/053140(Akiyoshi, K et al.).

Using a process similar to the one described in the preparation ofcompound 19, a sodium maltotriosemethylcarboxylate, characterized by adegree of substitution with sodium methylcarboxylate of 2.73, isfunctionalized with cholesteryl 2-aminoethylcarbamate.

According to the dry extract: [compound 25]=2.9 mg/g.

According to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with cholesteryl 2-aminoethylcarbamateis 0.28.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 2.45.

Compound 26: Sodium maltotriosemethylcarboxylate Functionalized withalpha-phenyiglycine

Using a process similar to the one described in the preparation ofcompound 18, but involving alpha-phenylglycine (Bachem), a sodiummaltotriosemethylcarboxylate, characterized by a degree of substitutionwith sodium methylcarboxylate of 1.64, is functionalized withalpha-phenylglycine.

According to the dry extract: [compound 26]=9.1 mg/g.

According to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with alpha-phenylglycine is 0.52.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 1.12.

Compound 27: Sodium maltotriosemethylcarboxylate Functionalized with2-[(2octanoylamino-6-octanoylamino)hexanoylamino]ethanamine

The methyl ester of N,N-bis(octanoyl)lysine is obtained according to theprocess described in the publication Pal, A et al., Tetrahedron 2007,63, 7334-7348, from the methyl ester of L-lysine, hydrochloric acid salt(Bachem) and from octanoic acid (Sigma). The2-[(2-octanoylamino-6-octanoylamino)hexanoylamino]ethanamine is obtainedaccording to the process described in U.S. Pat. No. 2,387,201 (Weiner etal.), from the methyl ester of N,N-bis(octanoyl)lysine and fromethylenediamine (Roth).

Using a process similar to the one described in the preparation ofcompound 21, a sodium maltotriosemethylcarboxylate, characterized by adegree of substitution with sodium methylcarboxylate of 1.64, isfunctionalized with2-[(2-octanoylamino-6-octanoylamino)hexanoylamino]ethanamine.

According to the dry extract: [compound 27]=3.8 mg/g.

According to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with2-[(2-octanoylamino-6-octanoylamino)hexanoylamino]ethanamine is 0.28.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 1.36.

Compound 28: Sodium maltotriosemethylcarboxylate Functionalized withL-tyrosine

Using a process similar to the one described in the preparatiaon ofcompound 1, but involving methyl tyrosinate, hydrochloric acid salt(Bachem), a sodium maltotriosemethylcarboxylate, characterized by adegree of substitution with sodium methylcarboxylate of 1.64, isfunctionalized with tyrosine.

According to the dry extract: [compound 28]=9.1 mg/g.

According to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with L-tyrosine is 0.81.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 0.83.

Compound 29: Sodium maltotriosemethylcarboxylate Functionalized with2-aminoethyl dodecanoate

The 2-aminoethyl dodecanoate, para-toluenesulfonic acid salt, isobtained according to the process described in U.S. Pat. No. 4,826,818(Kenji M et al.), from dodecanoic acid (Sigma) and from ethanolamine(Sigma).

Using a process similar to the one described in the preparation ofcompound 21, a sodium maltotriosemethylcarboxylate, characterized by adegree of substitution with sodium methylcarboxylate of 1.64, isfunctionalized with 2-aminoethyl dodecanoate.

According to the dry extract: [compound 29]=1.8 mg/g.

According to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with 2-aminoethyl dodecanoate is 0.27.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 1.37.

Compound 30: Sodium maltotriosemethylcarboxylate Functionalized with3,7-dimethyloctanoyl phenylalaninate

The 3,7-dimethyloctanoyl phenylalaninate, para-toluenesulfonic acidsalt, is prepared from 3,7-dimethyloctan-1-ol and from L-phenylalanineaccording to the process described in U.S. Pat. No. 4,826,818 (Kenji etal.).

Using a process similar to the one described in the preparation ofcompound 21, a sodium maltotriosemethylcarboxylate, characterized by adegree of substitution with sodium methylcarboxylate of 1.64, isfunctionalized with 3,7-dimethyloctanoyl phenylalaninate.

According to the dry extract: [compound 30]=3.3 mg/g.

According to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with 3,7-dimethyloctanoylphenylalaninate is 0.39.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 1.25.

Compound 31: Sodium hyaluronate tetrasaccharide Functionalized withmethyl phenylalaninate

A solution of 4-mer sodium hyaluronate (Contipro Biotech) at 30 g/I isacidified on a Purolite (anionic) resin in order to obtain an aqueoushyaluronic acid solution of which the pH is brought to 7.1 by adding anaqueous solution (40%) of tetrabutylammonium hydroxide (Sigma). Thesolution is then lyophilized for 18 hours.

30 mg of tetrabutylammonium hyaluronate (48 μmol of tetrabutylammoniumcarboxylate functions) are solubilized in DMF. 5 mg of methylphenylalaninate (24 μmol), 6 mg of triethylamine (60 μmol) and 9 mg of2-chloro-1-methylpyridinium iodide (Sigma, 36 μmol) are added at 0° C.and the medium is then stirred at 20° C. for 16 hours. The solution isevaporated and the residue is analyzed by ¹H NMR in D₂O in order todetermine the degree of acid functions functionalized with methylphenylalaninate.

According to the ¹H NMR: the degree of substitution with carboxylatesfunctionalized with methyl phenylalaninate per saccharide unit is 0.22.

The degree of substitution with sodium carboxylates per saccharide unitis 0.28.

Compound 32: Sodium maltotriosemethylcarboxylate Functionalized with2-[(2-decanoylamino-6-decanoylamino)hexanoylamino]ethanamine

The methyl ester of N,N-bis(decanoyl)lysine is obtained according to theprocess described in the publication Pal, A et al., Tetrahedron 2007,63, 7334-7348, from the methyl ester of L-lysine, hydrochloric acid salt(Bachem) and from decanoic acid (Sigma). The2-[(2-decanoylamino-6-decanoylamino)hexanoylamino]ethanamine is obtainedaccording to the process described in U.S. Pat. No. 2,387,201 (Weiner etal.), from the methyl ester of N,N-bis(decanoyl)lysine and fromethylenediamine (Roth).

Using a process similar to the one described in the preparation ofcompound 21, a sodium maltotriosemethylcarboxylate, characterized by adegree of substitution with sodium methylcarboxylate of 1.64, isfunctionalized with2-[(2-decanoylamino-6-decanoylamino)hexanoylamino]ethanamine.

According to the dry extract: [compound 32]=3.9 mg/g.

According to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with2-[(2-decanoylamino-6-decanoylamino)hexanoylamino]ethanamine is 0.21

The degree of substitution with sodium methylcarboxylates per glucosideunit is 1.43.

Compound 33: Sodium maltotriosemethylcarboxylate Functionalized withε-N-dodecanoyl-L-lysine

The ethyl ester of ε-N-dodecanoyl-L-lysine, hydrochloric acid salt, isprepared from dodecanoic acid (Sigma) and from the ethyl ester ofL-lysine, hydrochloric acid salt (Bachem), according to the processdescribed in U.S. Pat. No. 4,126,628 (Paquet AM).

Using a process similar to the one described in the preparation ofcompound 1, a sodium maltotriosemethylcarboxylate, characterized by adegree of substitution with sodium methylcarboxylate of 1.64, isfunctionalized with E-N-dodecanoyl-L-lysine.

According to the dry extract: [compound 33]=4.2 mg/g.

According to the ¹H NMR: the degree of substitution withmethylcarboxylates functionalized with E-N-dodecanoyl-L-lysine is 0.37.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 1.27.

Compound 34: Sodium N-phenylalaninate mannitol 2,3,4,5-tetracarbamate

1,6-ditriisopropylsilyl mannitol is obtained according to the processdescribed in the publication Bhaskar, V et al., Journal of CarbohydrateChemistry 2003, 22(9), 867-879.

Using a process similar to the one described for the preparation ofcompound 7, [1,6-ditriisopropylsilyl-2,3,4,5-tetra(sodiumN-phenylalaninate carbamate)]mannitol is obtained.

Using a process similar to the one described in the publication PJEdwards et al., Synlett 1995, 9, 898-900, the triisopropylsilyl groupsare deprotected in order to give N-phenylalanine acid mannitol2,3,4,5-tetracarbamate.

Using a process similar to the one described for the preparation ofcompound 7, sodium N-phenylalaninate mannitol 2,3,4,5-tetracarbamate isthen obtained.

¹H NMR (D₂O, ppm): 2.6-3.25 (8H); 3.6-4.3 (8H); 4.75-5.0 (4H); 6.9-7.5(24H).

Counterexample A1: Sodium dextranmethylcarboxylate Functionalized withL-phenylalanine

A sodium dextranmethylcarboxylate functionalized with L-phenylalanine issynthesized from a dextran having a weight-average molar mass of 1kg/mol (Pharmacosmos, average degree of polymerization of 3.9) accordingto a process similar to the one described in application WO 2012/153070.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 1.0

The degree of substitution with methylcarboxylates functionalized withL-phenylalanine per glucoside unit is 0.65.

Counterexample A2: Sodium dextranmethylcarboxylate Functionalized withL-phenylalanine

A sodium dextranmethylcarboxylate functionalized with L-phenylalanine issynthesized from a dextran having a weight-average molar mass of 5kg/mol (Pharmacosmos, average degree of polymerization of 19) accordingto a process similar to the one described in application WO 2010/122385.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 0.98.

The degree of substitution with methylcarboxylates functionalized withL-phenylalanine per glucoside unit is 0.66.

Counterexample B1: Sodium dextranmethylcarboxylate Functionalized withcholesteryl leucinate

A sodium dextranmethylcarboxylate functionalized with cholesterylleucinate is synthesized from a dextran having a weight-average molarmass of 1 kg/mol (Pharmacosmos, average degree of polymerization of 3.9)according to a process similar to the one described in application WO2012/153070.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 1.64.

The degree of substitution with methylcarboxylates functionalized withcholesteryl leucinate per glucoside unit is 0.05.

Counterexample B2: Sodium dextranmethylcarboxylate Functionalized withcholesteryl leucinate

A sodium dextranmethylcarboxylate functionalized with cholesterylleucinate is synthesized from a dextran having a weight-average molarmass of 5 kg/mol (Pharmacosmos, average degree of polymerization of 19)according to a process similar to the one described in application WO2010/041119.

The degree of substitution with sodium methylcarboxylates per glucosideunit is 1.60.

The degree of substitution with methylcarboxylates functionalized withcholesteryl leucinate per glucoside unit is 0.04.

B. Turbidity Measurement Assays

The turbidity of solutions in which a “model” protein, lysozyme andeither a compound according to the invention or a counterexamplecompound are brought together is analyzed in the compound/lysozyme molarratios of 0, 0.1 and 0.5.

The following solutions are prepared beforehand: histidine buffersolution, pH 6.2±0.1, at 194 mM (30 mg/ml), sodium chloride (NaCl)solution at 5017 mM (293 mg/ml), solution of lysozyme (Sigma-Aldrich,Ref L6876, CAS#12650-88-3) at 15 mg/ml (0.35 mM), and solutions of eachof the test products (pH 6.2±0.1), i.e. compounds according to theinvention and counterexamples.

For each of the solutions of compounds to be prepared, 3 ml of anaqueous solution of compound are adjusted to pH 6.2±0.1 using 50±25 μlof a 0.1N hydrochloric acid (HCl) solution.

The solutions of the compounds tested are detailed in the followingtable 3.

TABLE 3 Final concentration pH of the compounds of the final Productstested (mM) solutions Compound 1 6.8 6.3 Counter example A1 27.2 6.2Counter example A2 5.4 6.3 Compound 13 9.6 6.3 Counter example B1 10.76.2 Counter example B2 5.3 6.3

The test solutions at the compound/lysozyme molar ratios: 0, 0.1 and 0.5are then prepared as follows.

The sodium chloride (NaCl) solution at 5017 mM, the histidine buffersolution at 194 mM and then the solution of compound are successivelyadded to water, which results in a mixture which is homogenized on aroller mixer (Stuart Roller Mixer SRT9D) for 1 minute.

The lysozyme solution is, finally, added and then the final mixture ishomogenized on the roller mixer for 1 minute.

The turbidity (expressed in NTU) for each of the final test solutions ismeasured using a HACH 2100AN turbidity meter.

The turbidity of the compound 1/lysozyme solution is analyzed incomparison with that of the counterexample A1/lysozyme andcounterexample A2/lysozyme solutions. The turbidity of the compound13/lysozyme solution is analyzed in comparison with that of thecounterexample B1/lysozyme and counterexample B2/lysozyme solutions. Theresults are shown in the following table 4.

TABLE 4 Turbidity of the Turbidity of the Turbidity of the solutions atthe solutions at the solutions at the molar ratio 0 molar ratio 0.1molar ratio 0.5 (NTU) (NTU) (NTU) Compound 1 - I 55 4.8 lysozymesolution 0 Counter example A1 - 0 161 2480 lysozyme solution Counterexample A2 - 0 1293 9386 lysozyme solution Compound 13 - 0 32 395lysozyme solution Counter example B1 - 0 90 768 lysozyme solutionCounterexample B2 - 0 1824 Saturation lysozyme solution

The turbidity of the compound 1/lysozyme solution is lower than that ofthe counterexample compound A1/lysozyme and counterexample compoundA2/lysozyme solutions, whatever the ratio.

The turbidity of the compound 13/lysozyme solution is lower than that ofthe counterexample compound B1/lysozyme and counterexample compoundB2/lysozyme solutions, whatever the ratio.

C. Interaction with Albumin

It is known that the prior art compounds which do not make it posisbleto obtain nonturbid solutions with lysozyme, interact with proteins, inparticular with “model” proteins such as albumin.

In order to determine, following the results obtained with the compoundsaccording to the invention in the test with lysozyme (i.e. turbiditymeasurement assays previously described), whether there are nevertheless“model” proteins with which the compounds according to the invention mayinteract, a test for interaction with albumin was carried out.

The test carried out is a “fluorescence” test with albumin, which makesit posible, by measuring the variations in fluorescence of albumin, toverify whether an interaction exists between the compound tested andalbumin.

The compound/albumin solutions are prepared from stock solutions ofcompounds and of serum albumin (BSA) by mixing the appropriate volumesin order to obtain a fixed BSA concentration at 0.5 mg/ml andcompound/BSA weight ratios of 1, 5 and 10. These solutions are preparedin a PBS buffer at pH 7.4.

200 μl of the various compound/BSA solutions are introduced into a96-well plate. The fluorescence measurements are carried out at roomtemperature (20° C.) with an EnVision® fluorescence spectrometer(PerkinElmer). The excitation wavelength is 280 nm and the emissionwavelength is 350 nm. This corresponds to the fluorescence of thetryptophan residues of albumin (Ruiz-Peña M. et al., M, A.Physico-chemical studies of molecular interactions between non-ionicsurfactants and bovine serum albumin, Colloids Surf. B Biointerfaces2010, 75, 282-289). The F (compound/BSA)/F0 (BSA alone) ratio makes itpossible to evaluate the interaction between the compound and albumin.If this ratio is less than 1, this means that the compound inducespartial quenching of the albumin fluorescence linked to a change inenvironment of the tryptophan residues. This change reflects aninteraction between the compound and albumin. It was verified, as acontrol, that, for all the compounds tested, the fluorescence of thecompound alone is negligible considering the fluorescence of albumin(fluorescence (compound) <2% fluorescence (albumin)). The results aregiven in table 5.

TABLE 5 Compound/BSA Result Result Compound weight ratio F/F0 <0.5 F/F0<0.85 19 1 YES — 20 1 YES — 21 1 YES — 22 1 YES — 23 1 YES — 27 1 YES —29 1 YES — 30 1 YES — 2 1 NO NO 5 NO YES 10 NO YES

The results show that all the compounds interact with albumin.

As regards compounds 19 to 30, they cause a decrease in the fluorescenceratio such that F/F0<0.5 at a compound/BSA weight ratio of 1.

As regards compound 2, it decreases the fluorescence ratio such thatF/F0<0.85 at a compound/BSA weight ratio of 5 and of 10.

What is claimed is:
 1. Substituted anionic compounds, in isolated formor as a mixture, consisting of a backbone made up of a discrete number uof between 1 and 8 (1≦u≦8) of identical or different saccharide units,linked via identical or different glycosidic bonds, said saccharideunits being chosen from the group consisting of hexoses in cyclic formor in open reduced form, characterized in that they are substitutedwith: c) at least one substituent of general formula V:—[R₁]_(a)-[AA]_(m)   formula V the substituents being identical ordifferent when there are at least two substituents, in which: theradical -[AA]- denotes an amino acid residue, the radical —R₁— being:either a bond and then a=0, and the amino acid residue -[AA] is directlybonded to the backbone via a function G_(a), or a C₂ or C₁₅ carbon-basedchain, and then a=1, which is optionally substituted and/or comprisingat least one heteroatom chosen from O, N and S and at least one acidfunction before the reaction with the amino acid, said chain forming,with the amino acid residue -[AA], an amide function, and is attached tothe backbone by means of a function F_(a) resulting from a reactionbetween a hydroxyl function borne by the backbone and a function or asubstituent borne by the precursor of the radical —R₁—, F_(a) is afunction chosen from ether, ester or carbamate functions, G_(a) is acarbamate function, m is equal to 1 or 2, the degree of substitution ofthe saccharide units, j, with —[R₁]_(a)-[AA]_(m) being strictly greaterthan 0 and less than or equal to 6, 0<j≦6; d) and, optionally, one ormore substituents —R′₁, the substituent —R′₁ being a C₂ to C₁₅carbon-based chain which is optionally substituted and/or comprising atleast one heteroatom chosen from O, N and S and at least one acidfunction in the form of an alkali metal cation salt, said chain beingbonded to the backbone via a function F′_(a) resulting from a reactionbetween a hydroxyl function or a carboxylic acid function borne by thebackbone and a function or a substituent borne by the precursor of thesubstituent —R′₁, F′_(a) is an ether, ester or carbamate function, thedegree of substitution of the saccharide units, i, with —R′₁, beingbetween 0 and 6-j, 0≦i≦6-j and, F_(a) and F_(a)′ are identical ordifferent, F_(a) and G_(a) are identical or different, i+j≦6, —R′₁identical to or different than —R₁—, the free salifiable acid functionsborne by the substituent —R′₁ are in the form of alkali metal cationsalts, said identical or different glycosidic bonds being chosen fromthe group consisting of glycosidic bonds of (1,1), (1,2), (1,3), (1,4)or (1,6) type, in an alpha or beta geometry.
 2. The anionic compounds asclaimed in claim 1, wherein the radical —R₁ is chosen from the followinggroups, in which*represents the site of attachment to F_(a):

or their salts of alkali metal cations chosen from the group consistingof Na⁺ or K⁺.
 3. The anionic compounds as claimed in claim 1, whereinthe radical —R₁— before attachment to the radical [AA] is —CH₂—COOH. 4.The anionic compounds as claimed in claim 1, wherein the radical —R′₁ ischosen from the following groups, in which*represents the site ofattachment to F′_(a):

or their salts of alkali metal cations chosen from the group consistingof Na⁺ or K⁺.
 5. The anionic compounds as claimed in claim 1, whereinthe radical —R′₁ is a radical —CH₂COOH.
 6. The anionic compounds asclaimed in claim 1, wherein the amino acids are chosen from alpha-aminoacids.
 7. The anionic compounds as claimed in claim 6, wherein thealpha-amino acids are chosen from natural alpha-amino acids.
 8. Theanionic compounds as claimed in claim 7, wherein the natural alpha-aminoacids are chosen from hydrophobic amino acids chosen from the groupcomprising tryptophan, leucine, alanine, isoleucine, glycine,phenylalanine, tyrosine and valine, in their L, D or racemic forms. 9.The anionic compounds as claimed in claim 7, wherein the naturalalpha-amino acids are chosen from polar amino acids chosen from thegroup comprising aspartic acid, glutamic acid, lysine and serine, intheir L, D or racemic forms.
 10. The anionic compounds as claimed inclaim 6, wherein the alpha-amino acid is chosen from the groupconsisting of alpha-methylphenylalanine, alpha-methyltyrosine,O-methyltyrosine, alpha-phenylglycine, 4-hydroxyphenylglycine and3,5-dihydroxyphenylglycine, in their L, D or racemic forms.
 11. Theanionic compounds as claimed in claim 1, wherein at least one saccharideunit is in cyclic form.
 12. The anionic compounds as claimed in claim 1,wherein at least one saccharide unit is in open reduced form.
 13. Theanionic compounds as claimed in claim 1, wherein the backbone is made upof a discrete number of between 3 and 5 saccharide units.
 14. Theanionic compounds as claimed in claim 1, wherein the backbone is made upof a discrete number u=3 saccharide units.
 15. The anionic compounds asclaimed in claim 1, wherein the backbones are obtained by enzymaticdegradation of a polysaccharide followed by purification.
 16. Theanionic compounds as claimed in claim 1, wherein the backbones areobtained by chemical degradation of a polysaccharide followed bypurification.
 17. The anionic compounds as claimed in claim 1, whereinthe backbones are obtained chemically, by covalent coupling oflower-molecular-weight precursors.
 18. A pharmaceutical compositionwhich comprises an anionic compound as claimed in claim 1 and an activeingredient chosen from the group consisting of proteins, glycoproteins,peptides and nonpeptide therapeutic molecules.